Negative electrode active material and power storage device

ABSTRACT

A power storage device with high capacity is provided. Alternatively, a power storage device with excellent cycle characteristics is provided. Alternatively, a power storage device with high charge and discharge efficiency is provided. Alternatively, a power storage device with a long lifetime is provided. A negative electrode active material includes a first region and a second region. The first region includes at least one element selected from Si, Mg, Ca, Ga, Al, Ge, Sn, Pb, Sb, Bi, Ag, Zn, Cd, As, Hg, and In. The second region includes oxygen and the same element as the one included in the first region. The crystallite size of the element included in the first region is larger than or equal to 1 nm and smaller than or equal to 10 nm.

TECHNICAL FIELD

The present invention relates to an object, a method, or a manufacturingmethod. In addition, the present invention relates to a process, amachine, manufacture, or a composition of matter. In particular, oneembodiment of the present invention relates to a semiconductor device,display device, a light-emitting device, a power storage device, astorage device, a driving method thereof, or a manufacturing methodthereof. In particular, one embodiment of the present invention relatesto a power storage device and a manufacturing method thereof.

BACKGROUND ART

In recent years, secondary batteries such as lithium-ion secondarybatteries, lithium-ion capacitors, and air cells have been activelydeveloped. In particular, demand for lithium-ion secondary batterieswith high output and high energy density has rapidly grown with thedevelopment of the semiconductor industry, for electronic devices, forexample, portable information terminals such as cell phones,smartphones, and laptop computers, portable music players, and digitalcameras; medical equipment; next-generation clean energy vehicles suchas hybrid electric vehicles (HEVs), electric vehicles (EVs), and plug-inhybrid electric vehicles (PHEVs); and the like. The lithium-ionsecondary batteries are essential as rechargeable energy supply sourcefor today's information society.

There is a very great need for more compact and higher capacitylithium-ion secondary batteries. Thus electrodes formed of analloy-based material of silicon, tin, or the like, instead of a carbonmaterial such as graphite (black lead) which has been conventionallyused as a negative electrode active material, have been activelydeveloped. The (graphite has a theoretical capacity of 372 mAh/g,whereas the negative electrode of silicon has a dramatically hightheoretical capacity of 4200 mAh/g, and therefore silicon is an optimalmaterial for higher capacity lithium-ion secondary batteries.

However, when the material that is alloyed and dealloyed with lithium(e.g., silicon) greatly expands and contracts with reception and releaseof carrier ions in charge and discharge cycles; therefore, when theamount of carrier ions received by the material increases, the contactstates between an active material and a conductive additive, betweenactive materials, and between an active material and a current collectorbecome worse and a conductive path is lost in some cases. The loss ofthe conductive path decreases the capacity as charge and dischargecycles increase. Moreover, in some cases, silicon is deformed or brokento be separated from a current collector or pulverized, so that afunction as a lithium-ion secondary battery becomes difficult tomaintain.

Patent Document 1 discloses a silicon layer that is formed over anuneven current collector so that a stress due to expansion orcontraction of the silicon is reduced.

REFERENCE Patent Document

[Patent Document 1] Japanese Published Patent Application No.2013-235811

DISCLOSURE OF INVENTION

An object of one embodiment of the present invention is to provide apower storage device having high capacitance. Another object of oneembodiment of the present invention is to provide a power storage devicewith excellent cycle characteristics. Another object of one embodimentof the present invention is to provide a power storage device with highcharge and discharge efficiency. An object of one embodiment of thepresent invention is to provide a long-life power storage device.

An object of one embodiment of the present invention is to reduce orinhibit the decomposition reaction of an electrolytic solution, whichspeeds up at high temperature, and to prevent a decrease in charge anddischarge capacity in charging and discharging at high temperature, inorder to extend the operating temperature range of a power storagedevice. An object of one embodiment of the present invention is toprovide a novel power storage device.

In the case where a power storage device such as a secondary battery isused in a flexible display device, a flexible electronic device, or thelike, the power storage device is provided in a flexible portion (partor the whole of a housing). In this case, the power storage device isbent with the flexible portion, so that repeated change in the form ofthe power storage device might cause separation between a currentcollector and an active material in the power storage device. As aresult, deterioration of the power storage device might be promoted.

Another object of one embodiment of the present invention is to preventdeterioration of a power storage device caused by change in its form.

Note that the descriptions of these objects do not disturb the existenceof other objects. In one embodiment of the present invention, there isno need to achieve all the objects. Other objects will be apparent fromand can be derived from the description of the specification, thedrawings, the claims, and the like.

One embodiment of the present invention is a negative electrode activematerial including a first region and a second region. The first regionincludes at least one element selected from Si, Mg, Ca, Ga, Al, Ge, Sn,Pb, Sb, Bi, Ag, Zn, Cd, As, Hg, and In. The second region includesoxygen and the same element as the one included in the first region. Thecrystallite size of the element included in the first region is largerthan or equal to 1 nm and smaller than or equal to 10 nm. The secondregion may include oxide of the same element as the one included in thefirst region. Here, the crystallite size of the element included in thefirst region means the crystallite size of a single crystal, apolycrystal, or a microcrystal of the element included in the firstregion.

Another embodiment of the prevent invention is a negative electrodeactive material including silicon and silicon oxide. The crystallitesize of silicon included in the negative electrode active material islarger than or equal to 1 nm and smaller than or equal to 10 nm.

Another embodiment of the present invention is a negative electrodeactive material including silicon and silicon oxide. The averageparticle size of the negative electrode active material is preferablylarger than or equal to 30 nm and smaller than or equal to 30 μm, morepreferably larger than or equal to 100 nm and smaller than or equal to20 μm, further preferably larger than or equal to 500 nm and smallerthan or equal to 10 μm, or still further preferably larger than or equalto 1 μm and smaller than or equal to 6 μm. The crystallite size ofsilicon included in the negative electrode active material is largerthan or equal to 1 nm and smaller than or equal to 10 nm.

The crystallite size in the above structures is preferably obtained byan X-ray diffraction method.

Another embodiment of the present invention is a negative electrodeactive material including silicon and silicon oxide. When the atomicratio of silicon and oxygen of the silicon oxide is expressed asSi:O=x:y, the silicon oxide includes a region of x<y.

Another embodiment of the present invention is a power storage deviceincluding the negative electrode active material described in any one ofthe above paragraphs. The power storage device includes a positiveelectrode and a negative electrode. The negative electrode includes anegative electrode current collector and the negative electrode activematerial. The negative electrode active material is between the negativeelectrode current collector and the positive electrode. In thisstructure, silicon included in the negative electrode active material ispreferably in contact with the negative electrode current collector. Inaddition, in this structure, silicon oxide included in the negativeelectrode active material is preferably in contact with the negativeelectrode current collector.

One embodiment of the present invention can provide a power storagedevice having high capacitance. One embodiment of the present inventioncan provide a power storage device with excellent cycle characteristics.One embodiment of the present invention can provide a power storagedevice with high charge and discharge efficiency. One embodiment of thepresent invention can provide a long-life power storage device.

One embodiment of the present invention makes it possible to reduce orinhibit the decomposition reaction of an electrolytic solution, whichspeeds up at high temperature, and to prevent a decrease in charge anddischarge capacity in charge and discharge at high temperature, so thatthe operating temperature range of a power storage device can beextended. One embodiment of the present invention can provide a novelpower storage device.

One embodiment of the present invention can prevent deterioration of apower storage device caused by change in its form.

Note that the description of these effects does not disturb theexistence of other effects. In one embodiment of the present invention,there is no need to obtain all the effects. Other effects will beapparent from and can be derived from the description of thespecification, the drawings, the claims, and the like.

BRIEF DESCRIPTION OF DRAWINGS

In the accompanying drawings:

FIGS. 1A to 1C illustrate an active material of one embodiment of thepresent invention;

FIGS. 2A and 2B illustrate an active material of one embodiment of thepresent invention;

FIGS. 3A and 3B illustrate a negative electrode of one embodiment of thepresent invention;

FIG. 4 illustrates an electrode of one embodiment of the presentinvention;

FIG. 5 is an external view of a thin storage battery;

FIGS. 6A and 6B are cross sectional views of a thin storage battery;

FIGS. 7A and 7B show a method for fabricating a thin storage battery;

FIGS. 8A and 8B show a method for fabricating a thin storage battery;

FIG. 9 shows a method for fabricating a thin storage battery;

FIGS. 10A to 10C illustrate the radius of curvature on a plane;

FIGS. 11A to 11D illustrate the radius of curvature of a film;

FIGS. 12A and 12B illustrate a coin-type storage battery;

FIGS. 13A and 13B illustrate a cylindrical storage battery;

FIGS. 14A to 14C illustrate an example of a storage battery;

FIGS. 15A to 15C illustrate an example of a storage battery;

FIGS. 16A and 16B illustrate an example of a power storage system;

FIGS. 17A1, 17A2, 17B1, and 17B2 illustrate an example of a powerstorage system;

FIGS. 18A and 18B illustrate an example of a power storage system;

FIGS. 19A to 19G illustrate examples of electronic devices;

FIGS. 20A to 20C illustrate an example of an electronic device;

FIG. 21 illustrates examples of electronic devices;

FIGS. 22A and 22B illustrate examples of vehicles;

FIGS. 23A and 23B show operation of a secondary battery;

FIGS. 24A to 24C show results of X-ray diffraction measurement;

FIGS. 25A to 25C show cross-sectional STEM images and a cross-sectionalTEM image;

FIGS. 26A and 26B show a cross-sectional TEM image and a selected areadiffraction pattern;

FIGS. 27A and 27B show cross-sectional TEM images;

FIGS. 28A and 28B show a cross-sectional TEM image and a selected areadiffraction pattern;

FIGS. 29A and 29B show cross-sectional TEM images;

FIGS. 30A and 30B show a cross-sectional TEM image and a selected areadiffraction pattern;

FIG. 31 illustrates a method for forming an electrode;

FIGS. 32A and 32B show results of charge and discharge measurement on astorage battery;

FIG. 33 shows a result of charge and discharge measurement on a storagebattery;

FIGS. 34A to 34C show SEM images;

FIGS. 35A to 35C show SEM images;

FIGS. 36A to 36C show SEM images;

FIGS. 37A to 37C show charge and discharge cycle performance of storagebatteries;

FIGS. 38A to 38C show charge and discharge efficiency of storagebatteries.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments and examples of the present invention will bedescribed in detail with reference to the accompanying drawings.However, the present invention is not limited to the descriptions of theembodiments and examples and it is easily understood by those skilled inthe art that the mode and details can be changed variously. Accordingly,the present invention should not be interpreted as being limited to thecontent of the embodiments and examples below.

Note that in the drawings used in this specification, the thicknesses offilms, layers, and substrates and the sizes of components (e.g., thesizes of regions) are exaggerated for simplicity in some cases.Therefore, the sizes of the components are not limited to the sizes inthe drawings and relative sizes between the components.

Note that the ordinal numbers such as “first” and “second” in thisspecification and the like are used for convenience and do not denotethe order of steps, the stacking order of layers, or the like.Therefore, for example, description can be made even when “first” isreplaced with “second” or “third”, as appropriate. In addition, theordinal numbers in this specification and the like are not neccssarilythe same as those which specify one embodiment of the present invention.

Note that in structures of the present invention described in thisspecification and the like, the same portions or portions having similarfunctions are denoted by common reference numerals in differentdrawings, and descriptions thereof are not repeated. Further, the samehatching pattern is used for portions having similar functions, and theportions are not especially denoted by reference numerals in some cases.

Note that in this specification and the like, a positive electrode and anegative electrode for a power storage device may be collectivelyreferred to as an electrode; in this case, the electrode in this caserefers to at least one of the positive electrode and the negativeelectrode.

Note that the power storage device in this specification and the likeindicates all elements and devices that have the function of storingelectric power. For example, a storage battery such as a lithium-ionsecondary battery, a lithium-ion capacitor, and an electric double layercapacitor are included in the category of the power storage device.

Here, a charge rate and a discharge rate will be described. For example,in the case of charging a secondary battery with a capacity of X [Ah] ata constant current, a charge rate of 1 C means the current value I [A]with which charging is terminated in exactly 1 hour, and a charge rateof 0.2 C means I/5 [A] (i.e., the current value with which charging isterminated in exactly 5 hours). Similarly, a discharge rate of 1 C meansthe current value I [A] with which discharging is ended in exactly 1hour, and a discharge rate of 0.2 C means I/5 [A] (i.e., the currentvalue with which discharging is ended in exactly 5 hours).

Embodiment 1

In this embodiment, a negative electrode active material of oneembodiment of the present invention is described.

In the case where silicon, a material alloyed and dealloyed withlithium, is used as a negative electrode active material, a capacity canbe increased compared with the case where graphite, a conventionalnegative electrode active material, is used. Graphite has a theoreticalcapacity of 372 mAh/g, whereas silicon has a theoretical capacity of4200 mAh/g, that is over ten times as much as that of graphite.

However, a material that is alloyed and dealloyed with lithium (e.g.,silicon) greatly expands and contracts with reception and release ofcarrier ions in charge and discharge cycles; therefore, when the amountof carrier ions received by the material increases, deformation or acrack would be generated. Then, the active material might be separatedfrom a current collector or pulverized, which might lead to difficultyof maintaining a function for a lithium-ion secondary battery.Pulverization means that a material is repeatedly broken into piecesbecause of expansion and contraction, for example. If the material ispulverized, the material might be separated from the current collector,a separated piece thereof might get stuck in a gap of a separator ormight attached to a surface of a positive electrode, or phenomena likethat might occur. Moreover, because of the expansion and thecontraction, the contact states between an active material and aconductive additive, between active materials, and between an activematerial and a current collector become worse and a conductive path islost in some cases. The loss of the conductive path decreases thecapacity as charge and discharge cycles increase.

The reaction potential of the negative electrode active material ispreferably as low as possible, in which case the voltage of the powerstorage device can be high. On the other hand, when the reactionpotential is low, power of reducing an electrolyte is increased, so thatan organic solvent or the like in an electrolyte might be subjected toreductive decomposition. The range of potentials in which theelectrolysis of an electrolyte does not occur is referred to as apotential window. The electrode potential of the negative electrodeneeds to be within a potential window of an electrolyte; however, thepotentials of many active materials used for negative electrodes oflithium-ion secondary batteries and lithium-ion capacitors are out ofthe potential windows of almost all kinds of electrolytes. Specifically,materials with low reaction potentials, such as graphite and silicon,can increase the voltage of storage batteries but are likely to causethe reductive decomposition of electrolytes, which is problematic.

Note that in this specification and the like, an electrolytic solutionincluding a solvent and salts is referred to as an electrolyte in somecases.

To suppress deformation or a crack of the negative electrode activematerial due to expansion and contraction caused by reception andrelease of carrier ions, it is preferred to reduce a particle size ofthe negative electrode active material, for example. When the particlesize of the negative electrode active material is reduced, a surfacearea per unit weight of the negative electrode active material isincreased.

Meanwhile, a reaction between the electrolyte and the negative electrodeactive material occurs at the surface of the negative electrode activematerial. Therefore, as the surface area per unit weight of the negativeelectrode active material increases, the amount of the reaction betweenthe negative electrode active material and the electrolyte increases.

An active material of one embodiment of the present invention includes afirst region which expands and contracts by a reaction with carrierions, and a second region positioned between the first region and anelectrolyte. The second region is a region having small reactivity withcarrier ions, whereby decomposition of the electrolyte is suppressed anddeformation and a crack of the active material due to the reaction withcarrier ions are also suppressed.

A negative electrode active material of one embodiment of the presentinvention includes a first region and a second region. A particle of anegative electrode active material of one embodiment of the presentinvention preferably includes a first region and a second region.

The second region is preferably in contact with a surface of thenegative electrode active material at least partly. The second region ispreferably positioned to surround the first region.

The first region includes a material that reacts with carrier ions. Thefirst region is preferably a single crystal, or may have an amorphousregion in contact with the periphery of the single crystal. The firstregion may become amorphous after a reaction with carrier ions.Alternatively, the first region may be a polycrystal.

It is preferred that carrier ions can pass through the second region.The second region preferably has higher resistance than the firstregion. When the second region surrounds the first region, an area ofthe first region in contact with the electrolyte can be reduced.Compared with the case where the first region contacts with theelectrolyte, decomposition of the electrolyte can be suppressed in thecase where the second region contacts with the electrolyte because theresistance in the second region is higher than that in the first region.

In addition, reactivity with carrier ions in the second region ispreferably smaller than that in the first region. A capacity per unitweight or per unit volume in the second region is preferably smallerthan that in the first region. When the second region reacts withcarrier ions, expansion and contraction due to the reaction with carrierions in the second region are preferably milder than those in the firstregion. Because the expansion and contraction in the second region ismild, the second region can reduce a stress change of the activematerial caused by the expansion and contraction in the first region.

The second region is preferably amorphous. The second region may containan element that would be a carrier ion after reaction with carrier ions.

FIG. 1A is a schematic view illustrating a negative electrode activematerial of one embodiment of the present invention. A cross-sectionalview of the negative electrode active material is shown in FIG. 1A. Thecross-sectional view shows a cut surface at which the negative electrodeactive material is cut. In the example in FIG. 1A, a negative electrodeactive material 100 has a particle-like shape. The negative electrodeactive material 100 includes a first region 101 and a second region 102.

FIG. 1B shows an example where the first regions 101 are scattered inthe negative electrode active material 100. As shown in FIG. 1B, therecan be a plurality of first regions 101. Similarly, there can be aplurality of second regions 102.

Alternatively, as shown in FIG. 1C, the negative electrode activematerial 100 may include a third region 103 that surrounds the firstregion 101. Here, the third region 103 is preferably in contact with thefirst region 101.

FIGS. 1A to 1C show examples where the negative electrode activematerial 100 has the particle-like shape; however, the negativeelectrode active material 100 may have a plate-like shape, for example.

Although it is acceptable that part of the first region 101 is incontact with a surface of the negative electrode active material 100 asshown in FIG. 2A, it is preferred that the first region 101 be not incontact with the surface as shown in FIGS. 1A and 1B. Alternatively, asshown in FIG. 2B, the third region 103 may be included to surround thefirst region 101.

When the negative electrode active material 100 has the particle-likeshape, the particle size is preferably larger than or equal to 30 nm andsmaller than or equal to 30 μm, more preferably larger than or equal to100 nm and smaller than or equal to 20 μm, further preferably largerthan or equal to 500 nm and smaller than or equal to 10 μm, or stillfurther preferably larger than or equal to 1 μm and smaller than orequal to 6 μm, for example. The particle size means, for example, adiameter of a sphere whose volume is equal to the volume of theparticle, or a diameter of a circle whose area is equal to the area ofthe cross-section surface of the particle. The particle size may becalculated by a laser diffraction and scattering method or the like.

The first region of the negative electrode active material 100preferably contains at least one of Si, Mg Ca, Ga, Al, Ge, Sn, Pb, Sb,Bi, Ag, Zn, Cd, As, Hg, and In, for example. These elements each have ahigher capacity than carbon. In particular, silicon has a hightheoretical capacity of 4200 mAh/g. Therefore, silicon is preferablyincluded in the first region of the negative electrode active material100.

The first region of the negative electrode active material 100 mayinclude Mg₂Si, Mg₂Ge, Mg₂Sn, SnS₂, V₂Sn₃, FeSn₂, CoSn₂, Ni₃Sn₂, Cu₆Sn₅,Ag₃Sn, Ag₃Sb, Ni₂MnSb, CeSb₃, LaSn₃, La₃Co₂Sn₇, CoSb₃, InSb, SbSn, orthe like.

Alternatively, for the first region of the negative electrode activematerial 100, oxide such as titanium dioxide (TiO₂), lithium titaniumoxide (Li₄Ti₃O₁₂), lithium-graphite intercalation compound (Li_(x)C₆),niobium pentoxide (Nb₂O₅), tungsten oxide (WO₂), or molybdenum oxide(MoO₂), or Li_(3-x)M_(x)N (M=Co, Ni, or Cu) with a Li₃N structure, whichis a nitride containing lithium and a transition metal, can be used.

The second region of the negative electrode active material 100preferably includes a compound including the same element as the one inthe first region. For example, the second region may include oxide ofthe same element as the one included in the first region. Alternatively,the second region may include nitride, sulfide, phosphide, fluoride, orthe like of the same element as the one included in the first region.Alternatively the second region preferably includes oxygen and the sameelement as the one included in the first region.

For example, the first region of the negative electrode active material100 may include at least one element selected from Si, Mg, Ca, Ga, Al,Ge, Sn, Pb, Sb, Bi, Ag, Zn, Cd, As, Hg, and In, and the second regionmay include oxide of the same element as the one included in the firstregion. For example, the first region and the second region of thenegative electrode active material of one embodiment of the presentinvention include Si and silicon oxide, respectively. Alternatively, thefirst region and the second region of the negative electrode activematerial of one embodiment of the present invention include Sn and a tinoxide, respectively.

When the first region and the second region contain at least one elementselected from Si, Mg, Ca, Ga, Al, Ge, Sn, Pb, Sb, Bi, Ag, Zn, Cd, As,Hg, and In, concentration of the element in the first region ispreferably higher than that in the second region.

The negative electrode active material 100 may include a material whichcauses a conversion reaction in the first region or the second region.For example, transition metal oxide which does not cause an alloyingreaction with lithium, such as cobalt oxide (CoO), nickel oxide (NiO),or iron oxide (FeO), may be used for the negative electrode activematerial. Other examples of the material which causes a conversionreaction include oxide such as Fe₂O₃, CuO, Cu₂O, RuO₂, and Cr₂O₃,sulfide such as CoS_(0.89), NiS, and CuS, nitride such as Zn₃N₂, Cu₃N,and Ge₃N₄, phosphide such as NiP₂, FeP₂, and CoP₃, and fluoride such asFeF₃ and BiF₃.

The first region 101 and the second region 102 of the negative electrodeactive material 100 include, for example, Si and silicon oxide,respectively. The third region that surrounds the first region 101 maybe included in the negative electrode active material 100. Here, thethird region may include, for example, amorphous silicon.

A plurality of negative electrode active materials may be used. Forexample, the negative electrode active material 100 and a secondnegative electrode active material that includes a different materialfrom the negative electrode active material 100 may be used.Alternatively, three or more active materials may be used incombination.

For example, one or more of the above-mentioned materials that can beused for the negative electrode active material 100 may be used as thesecond active material.

The second active material may include, for example, a carbon-basedmaterial. Examples of the carbon-based material include graphite,graphitizing carbon (soft carbon), non-graphitizing carbon (hardcarbon), a carbon nanotube, graphene, carbon black, and the like.Examples of the graphite include artificial graphite such as meso-carbonmicrobeads (MCMB), coke-based artificial graphite, or pitch-basedartificial graphite and natural graphite such as spherical naturalgraphite.

For the second active material, Li_(3-x)M_(x)N (M is Co, Ni, or Cu) witha Li₃N structure, which is a nitride including lithium and a transitionmetal, can be used. For example, Li_(2.6)Co_(0.4)N₃ is preferablebecause of high charge and discharge capacity (900 mAh/g and 1890mAh/cm³). A nitride containing lithium and a transition metal ispreferably used, in which case lithium ions are contained in thenegative electrode active material and thus the negative electrodeactive material can be used in combination with a material for apositive electrode active material which does not contain lithium ions,such as V₂O₅ or Cr₃O₈. In the case of using a material containinglithium ions as a positive electrode active material, the nitridecontaining lithium and a transition metal can be used for the negativeelectrode active material by extracting the lithium ions contained inthe positive electrode active material in advance.

[Method, for Forming Negative Electrode Active Material]

An example of a method for forming the negative electrode activematerial 100 is described below. Here, a method for forming the negativeelectrode active material 100 where Si is included in the first regionand silicon oxide is included in the second region is explained.

A non-uniform concentration gradient is made by, for example, performingheat treatment or the like on a composition including silicon andoxygen, to form the first region and the second region. For example, atleast part of the composition including silicon and oxygen is melted andthen solidified, whereby silicon concentration is non-uniformlydistributed. That is, the first region with high silicon concentrationand the second region with lower silicon concentration than in the firstregion can be formed.

SiO powder can be used as the composition including silicon and oxygen,for example.

The composition including silicon and oxygen may be formed by anevaporation method, a sputtering method, a chemical vapor deposition(CVD) method, or the like.

When a sputtering method is used, the composition including silicon andoxygen can be formed using silicon as a target and oxygen as a gas.Alternatively, a silicon oxide can be used as a target.

Here, the first region is preferably microcrystal of silicon, forexample.

The heat treatment is performed with the use of a furnace, for example.The temperature of the heat treatment is preferably higher than or equalto 800° C. and lower than or equal to 1400° C., or more preferablyhigher than or equal to 900° C. and lower than or equal to 1200° C., forexample. The heat treatment time is preferably longer than or equal to30 minutes and shorter than or equal to 20 hours, or more preferablylonger than or equal to 1 hour and shorter than or equal to 5 hours, forexample. The temperature rising rate is preferably higher than or equalto 50° C./hour and lower than or equal to 1000° C./hour, or morepreferably higher than or equal to 100° C./hour and lower than or equalto 500° C./hour, for example. The temperature falling rate is higherthan or equal to 50° C./hour and lower than or equal to 500° C./hour,for example. Alternatively, a sample may be rapidly cooled when put inthe atmosphere at room temperature after the heat treatment. Theatmosphere for the heat treatment is an inert atmosphere, for example.As the inert atmosphere, a rare gas such as argon or a gas such asnitrogen or hydrogen is used, for example. Alternatively, a mixed gas ofthem or an oxygen atmosphere may be used. The pressure is an atmospherepressure or a reduced pressure (a pressure lower than the atmospherepressure), for example.

Alternatively, heating may be performed by laser light. When laser lightis used, the melted composition including silicon and oxygen may berapidly cooled. By rapid cooling of the composition including siliconand oxygen after meltage, smaller silicon crystals can be discretelyformed in some cases. Alternatively, more largely distorted silicon canbe formed by rapid cooling in some cases. The laser light may be excimerlaser light with a wavelength of 400 nm or less or the second harmonicor the third harmonic of YAG laser or YVO₄ laser, for example.

[Measurement by XRD]

A crystal structure of a substance can be estimated by X-raydiffraction. In addition, the lattice constant and the crystallite sizecan be calculated from an obtained diffraction spectrum.

Here, the negative electrode active material of one embodiment of thepresent invention is assumed to include an element A (A is at least oneof elements selected from Si, Mg, Ca, Ga, Al, Ge, Sn, Pb, Sb, Bi, Ag,Zn, Cd, As, Hg, and In), and an X-ray diffraction spectrum of thenegative electrode active material of one embodiment of the presentinvention is assumed to be measured. Analysis on the obtained X-raydiffraction spectrum is performed under assumption that the negativeelectrode active material of one embodiment of the present inventionincludes a crystal of the element A, thereby the crystallite size z [nm]of the element A can be calculated. The analysis range of the X-raydiffraction is approximately 15 mmφ, for example. Therefore, theobtained crystallite size z of the element A is estimated to be anaverage of data within a range of 15 mmφ.

Here, the crystallite size z is preferably larger than or equal to 1 nmand smaller than or equal to 10 nm, or larger than or equal to 2 nm andsmaller than or equal to 5 nm.

As the crystallite size is smaller, the stress due to expansion andcontraction caused by a reaction with carrier ions can be reduced, forexample. Therefore, a crack or deformation of the negative electrodeactive material by charging or discharging can be suppressed. Thus, adecrease in capacity caused by charge and discharge cycles can bereduced. That is, a power storage device manufactured with the use ofthe negative electrode active material can have a long lifetime.

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Embodiment 2

In this embodiment, an electrode including the negative electrode activematerial shown in Embodiment 1 is described.

[Structure of Negative Electrode]

FIG. 3A is an overhead view of a negative electrode 200, and FIG. 3B isa cross-sectional view of a portion surrounded by a dashed line in FIG.3A. The negative electrode 200 has a structure in which a negativeelectrode active material layer 202 is provided over a negativeelectrode current collector 201. Although the negative electrode activematerial layers 202 are provided so that the negative electrode currentcollector 201 is sandwiched therebetween in FIGS. 3A and 3B, thenegative electrode active material layer 202 may be formed over only onesurface of the negative electrode current collector 201. The negativeelectrode active material layer 202 includes a negative electrode activematerial. For the negative electrode active material, the negativeelectrode active material shown in Embodiment 1 can be used.

There is no particular limitation on the negative electrode currentcollector 201 as long as it has high conductivity without causing asignificant chemical change in a power storage device. For example, thenegative electrode current collector 201 can be formed using a metalsuch as stainless steel, gold, platinum, zinc, iron, nickel, copper,aluminum, titanium, tantalum, or manganese, an alloy thereof, sinteredcarbon, or the like. Alternatively, copper or stainless steel that iscoated with carbon, nickel, titanium or the like can be used to form thecurrent collectors. Alternatively, the negative electrode currentcollector 201 can be formed using an aluminum alloy to which an elementwhich improves heat resistance, such as silicon, neodymium, scandium, ormolybdenum, is added. Still alternatively, a metal element which formssilicide by reacting with silicon can be used. Examples of the metalelement which forms silicide by reacting with silicon include zirconium,titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum,tungsten, cobalt, nickel, and the like. The negative electrode currentcollector 201 can have any of various shapes including a foil-likeshape, a plate-like shape (sheet-like shape), a net-like shape, acylindrical shape, a coil shape, a punching-metal shape, anexpanded-metal shape, a porous shape, and a shape of non-woven fabric asappropriate. The negative electrode current collector 201 may be formedto have micro irregularities on the surface thereof in order to enhanceadhesion to the active material layer. The negative electrode currentcollector 201 preferably has a thickness of more than or equal to 5 μmand less than or equal to 30 μm.

The negative electrode active material layer 202 contains a negativeelectrode active material. An active material refers only to a materialthat relates to insertion and extraction of ions that are carriers. Inthis specification and the like, a material that is actually an “activematerial” and materials such as a conductive additive, a binder, and thelike are collectively referred to as an active material layer.

The negative electrode active material layer 202 may include aconductive additive. Examples of the conductive additive include naturalgraphite, artificial graphite such as mesocarbon microbeads, and carbonfiber. Examples of carbon fiber include mesophase pitch-based carbonfiber, isotropic pitch-based carbon fiber, carbon nanofiber, and carbonnanotube. Carbon nanotube can be formed by, for example, a vapordeposition method. Other examples of the conductive additive includecarbon materials such as carbon black (acetylene black (AB) andgraphene. Alternatively, metal powder or metal fibers of copper, nickel,aluminum, silver, gold, or the like, a conductive ceramic material, orthe like can be used.

Flaky graphene has the excellent electrical characteristic of highconductivity and the excellent physical properties of high flexibilityand high mechanical strength. For this reason, the use of graphene asthe conductive additive can increase the points and the area where thenegative electrode active materials are in contact with each other.

Note that graphene in this specification includes single-layer grapheneand multilayer graphene including two to hundred layers. Single-layergraphene refers to a one-atom-thick sheet of carbon molecules having πbonds. Graphene oxide refers to a compound formed by oxidation of suchgraphene. When graphene oxide is reduced to form graphene, oxygencontained in the graphene oxide is not entirely released and part of theoxygen remains in the graphene. When graphene contains oxygen, theproportion of oxygen in the graphene, which is measured by X-rayphotoelectron spectroscopy (XPS), is higher than or equal to 2 at. % andlower than or equal to 20 at. %, preferably higher than or equal to 3at. % and lower than or equal to 15 at. %.

The negative electrode active material layer 202 may include a binder.

As the binder, a material such as polyimide, polyvinylidene fluoride(PVdF), polystyrene, poly(methyl acrylate), poly(methyl methacrylate)(PMMA), sodium polyacrylate, polyvinyl alcohol (PVA), polyethylene oxide(PEO), polypropylene oxide, polyvinyl chloride, polytetrafluoroethylene,polyethylene, polypropylene, isobutylene, polyethylene terephthalate,nylon, or polyacrylonitrile (PAN) can be used.

As the binder, water-soluble polymers can be used. As the water-solublepolymers, a polysaccharide or the like can be used. As thepolysaccharide, a cellulose derivative such as carboxymethyl cellulose(CMC), methyl cellulose, ethyl cellulose, hydroxypropyl cellulose,diacetyl cellulose, or regenerated cellulose, starch, or the like can beused.

As the binder, a rubber material such as styrene-butadiene rubber (SBR),styrene-isoprene-styrene rubber, acrylonitrile-butadiene rubber,butadiene rubber, or ethylene-propylene-diene copolymer can be used. Anyof these rubber materials is more preferably used in combination withthe aforementioned water-soluble polymers.

A single binder may be used or plural kinds of binders may be used incombination.

[Method 1 for Forming Negative Electrode]

Next, a method for forming the negative electrode 200 is described.

In order to form the negative electrode active material layer 202,slurry is formed first. The slurry can be formed in such a manner thatthe above-described material for the negative electrode active materialto which a conductive additive, a binder, and the like are added asappropriate is mixed with a solvent, for example. As the solvent, forexample, water or N-methyl-2-pyrrolidone (NMP) can be used. Water ispreferably used in terms of the safety and cost.

The mixing can be performed with a mixer. Here, any of a variety ofmixers can be used as the mixer. For example, a planetary mixer, ahomogenizer, or the like can be used.

The negative electrode current collector 201 may be subjected to surfacetreatment. Examples of such surface treatment are corona dischargetreatment, plasma treatment, and undercoat treatment. The surfacetreatment can increase the wettability of the negative electrode currentcollector 201 with respect to the slurry. In addition, the adhesionbetween the negative electrode current collector 201 and the negativeelectrode active material layer 202 can be increased.

Here, the “undercoat” refers to a film formed over a current collectorbefore application of slurry onto the current collector for the purposeof reducing the interface resistance between an active material layerand the current collector or increasing the adhesion between the activematerial layer and the current collector. Note that the undercoat is notnecessarily formed in a film shape, and may be formed in an islandshape. In addition, the undercoat may serve as an active material tohave capacity. For the undercoat, a carbon material can be used, forexample. Examples of the carbon material include graphite, carbon blacksuch as acetylene black and ketjen black (registered mark) and a carbonnanotube.

Then, the formed slurry is applied to the negative electrode currentcollector 201.

For the application, a slot die method, a gravure method, a blademethod, or combination of any of them can be used, for example.

Then, the solvent is volatilized from the slurry applied to the negativeelectrode current collector 201 by a method such as ventilation dryingor reduced pressure (vacuum) drying, whereby the negative electrodeactive material layer 202 is formed. The solvent is preferablyvolatilized using, for example, a hot wind at a temperature higher thanor equal to 30° C. and lower than or equal to 160° C. Alternatively, thesolvent may be volatilized using a hot plate or the like. There is noparticular limitation on the atmosphere.

The thickness of the negative electrode active material layer 202 formedin the above-described manner is preferably greater than or equal to 5μm and less than or equal to 300 μm, or more preferably greater than orequal to 10 μm and less than or equal to 150 μm, for example. The amountof the active material in the negative electrode active material layer202 is preferably greater than or equal to 1 mg/cm² and less than orequal to 30 mg/cm², for example.

Note that the negative electrode active material layer 202 may be formedover only one surface of the negative electrode current collector 201,or the negative electrode active material layers 202 may be formed suchthat the negative electrode current collector 201 is sandwichedtherebetween. Alternatively, the negative electrode active materiallayers 202 may be formed such that part of the negative electrodecurrent collector 201 is sandwiched therebetween.

The negative electrode active material layer 202 may be pressed by acompression method such as a roll press method or a flat plate pressmethod so as to be consolidated.

Through the above steps, the negative electrode active material layer202 can be formed.

Note that the negative electrode active material layer 202 may bepredoped. There is no particular limitation on the method for predopingthe negative electrode active material layer 202. For example, thenegative electrode active material layer 202 may be predopedelectrochemically. For example, before the battery is assembled, thenegative electrode active material layer 202 can be predoped withlithium in an electrolytic solution described later with the use of alithium metal as a counter electrode.

[Method 2 for Forming Negative Electrode]

Here, as a more specific example of the method for forming the negativeelectrode 200, an example of using SiO powder as a negative electrodeactive material is described.

As the binder, the above-described binder can be used. Here, polyimide(PI), accurately a precursor of polyimide, is used as the binder. As theconductive additive, the above-mentioned conductive additive can beused. In this example, acetylene black is used as the conductiveadditive.

The proportion of the weight of the binder to the total weight of theactive material, the binder, and the conductive additive is preferablyhigher than or equal to 3 weight % and lower than or equal to 50 weight%, or more preferably higher than or equal to 5 weight % and lower thanor equal to 20 weight %. The proportion of the weight of the conductiveadditive to the total weight is preferably higher than or equal to 0.5weight % and lower than or equal to 40 weight %, more preferably higherthan or equal to 2 weight % and lower than or equal to 15 weight %.

First, SiO powder for the negative electrode active material andacetylene black (AB) are mixed, and a solvent is added bit by bit whilestirring is performed, so that a mixture is obtained. As the solvent,NMP is used. When the viscosity of the mixture is adjusted to be high byadding a small amount of NMP, mixing (kneading) with a mixer later canbe performed on the mixture with high viscosity. The kneading can weakencohesion of the SiO powder. In addition, dispersibility of SiO powderand AB can be increased.

Next, the obtained mixture is mixed with a mixer.

Next, the precursor of polyimide and NMP are added to the mixturesubjected to the mixing, and mixing is further performed with a mixer,so that the slurry to be applied to the electrode is obtained. Theproportion of the solid content of the slurry is preferably higher thanor equal to 35 weight % and lower than or equal to 85 weight %, or morepreferably higher than or equal to 45 weight % and lower than or equalto 80 weight %, for example. The proportion of the solid content meansthe proportion of the weight of materials other than the solvent to thetotal weight of the slurry.

Here, the mixing order of the materials is not limited to the onedescribed above. For example, the negative electrode active material,the conductive additive, and the binder may be mixed at a time.

After formed through the above steps, the slurry is applied to thenegative electrode current collector 201. Then, the solvent isvolatilized to obtain the negative electrode. The description in Method1 for forming negative electrode is referred to for the application andthe volatilization.

[Method 3 for Forming Negative Electrode]

As another example of the method for forming the negative electrode 200,an example using SiO powder and graphite for the negative electrodeactive material is shown. As the graphite, artificial graphite is usedhere. As the artificial graphite, mesocarbon microbeads, carbonaceousmesophase, or the like can be used. The surface area of the graphite ispreferably larger than or equal to 1 m²/g and smaller than or equal to20 m²/g, or more preferably larger than or equal to 1 m²/g and smallerthan or equal to 10 m²/g.

As the binder, the above-described binder can be used. In this example,CMC-Na and SBR are used as the binder. The polymerization degree ofCMC-Na is preferably, for example, higher than or equal to 100 and lowerthan or equal to 1000, more preferably higher than or equal to 500 andlower than or equal to 900, or still more preferably higher than orequal to 600 and lower than or equal to 800.

As the conductive additive, the above-described conductive additive canbe used. In this example, carbon fiber is used as the conductiveadditive.

The proportion of the weight of CMC-Na to the total weight of the activematerial, the binder, and the conductive additive is preferably, forexample, higher than or equal to 1 weight % and lower than or equal to 7weight %. The proportion of the weight of SBR to the total weight ispreferably, for example, higher than or equal to 1 weight % and lowerthan or equal to 7 weight %.

In addition, the proportion of graphite to SiO is preferably higher thanor equal to 3 weight % and lower than or equal to 15 weight %.

First, the SiO powder and the graphite for the negative electrode activematerial, the carbon fiber, and the CMC-Na powder are mixed with amixer. Next, water is added as a solvent and kneading is performed. Thekneading means mixing on a mixture with high viscosity. The kneading canweaken cohesion of the active material. In addition, dispersibility inthe active material and among the active material, the conductiveadditive, and CMC-Na can be increased.

Here, the mixing order of the materials is not limited to the onedescribed above. For example, it is acceptable that only the carbonfiber and the active material are mixed first, and then the CMC-Napowder is added thereto.

Next, an SBR aqueous dispersion liquid is added to the mixture, andmixing is performed with a mixer. Here, water may be further added asthe solvent.

Furthermore, water as the solvent is added to the mixture so that themixture has certain viscosity, and mixing is performed with a mixer toobtain the slurry to be applied to the electrode. The proportion of thesolid content of the slurry is preferably higher than or equal to 30weight % and lower than or equal to 80 weight %, or more preferablyhigher than or equal to 40 weight % and lower than or equal to 70 weight%, for example.

After formed through the above steps, the slurry is applied to thenegative electrode current collector 201. Then the solvent isvolatilized to obtain the negative electrode. The description in Method1 for forming negative electrode is referred to for the application andthe volatilization.

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Embodiment 3

In this embodiment, an example of a power storage device using theelectrode shown in Embodiment 2 is described.

[Thin Storage Battery]

FIG. 5 illustrates a thin storage battery as an example of a powerstorage device. When a flexible thin storage battery is used in anelectronic device at least part of which is flexible, the storagebattery can be bent as the electronic device is bent.

FIG. 5 illustrates the appearance of a thin storage battery 500. FIG. 6Ais a cross-sectional view taken along dashed-dotted line A1-A2 in FIG.5, and FIG. 6B is a cross-sectional view taken along dashed-dotted lineB1-B2 in FIG. 5. The thin storage battery 500 includes a positiveelectrode 503 including a positive electrode current collector 501 and apositive electrode active material layer 502, a negative electrode 506including a negative electrode current collector 504 and a negativeelectrode active material layer 505, a separator 507, an electrolyticsolution 508, and an exterior body 509. The separator 507 is providedbetween the positive electrode 503 and the negative electrode 506 in theexterior body 509. The exterior body 509 is filled with the electrolyticsolution 508. The positive electrode active material layer 502 and thenegative electrode active material layer 505 face each other with theseparator 507 therebetween. In the storage battery 500 shown in FIGS. 6Aand 6B, there are five pairs of the positive electrode active materiallayer 502 and the negative electrode active material layer 505 that faceeach other.

The negative electrode active material layer 505 includes the negativeelectrode active material shown in Embodiment 1. For the negativeelectrode 506, the negative electrode shown in Embodiment 2 ispreferably used.

[Operation of Storage Battery]

Here, operation of a storage battery will be described.

Here, the operating principle of a secondary battery is described usinga lithium-ion secondary battery as an example. Here, for example,LiFePO₄ and graphite are used as a positive electrode active materialand a negative electrode active material, respectively,

FIG. 23A illustrates connections between a lithium-ion secondary battery1500 and a charger 1122 when the lithium-ion secondary battery ischarged. In the case of charging the lithium-ion secondary battery, areaction expressed by Formula 1 occurs in a positive electrode.LiFePO₄→FePO₄+Li⁺ +e ⁻  [Formula 1]

In addition, a reaction expressed by Formula 2 occurs in the negativeelectrode.xC+Li⁺ +e ⁻→LiC_(x) x≥6  [Formula 2]

FIG. 23B illustrates connections between the lithium-ion secondarybattery 1500 and a load 1123 in the case of discharging the lithium-ionsecondary battery. In the case of discharging the lithium-ion secondarybattery, a reaction expressed by Formula 3 occurs in the positiveelectrode.FePO₄+Li⁺ +e ⁻→LiFePO₄  [Formula 3]

In addition, a reaction expressed by Formula 4 occurs in the negativeelectrode.LiC_(x) →xC+Li⁺ +e ⁻ x≥6  [Formula 4]

Next, components of the storage battery are explained. First, thestructure of the negative electrode 506 is described. For the negativeelectrode 506, the negative electrode shown in Embodiment 2 ispreferably used. For the negative electrode current collector 504, thenegative electrode current collector 201 shown in Embodiment 2 can beused. For the negative electrode active material layer 505, the negativeelectrode active material layer 202 shown in Embodiment 2 can be used.

[Structure of Positive Electrode]

Next, a structure of the positive electrode 503 will be described. Thepositive electrode 503 includes the positive electrode current collector501 and the positive electrode active material layer 502.

There is no particular limitation on the positive electrode currentcollector 501 as long as it has high conductivity without causing asignificant chemical change in a power storage device. For example, thepositive electrode current collector 501 can be formed using a metalsuch as stainless steel, gold, platinum, zinc, iron, nickel, copperaluminum, titanium, tantalum, or manganese, an alloy thereof, sinteredcarbon, or the like. Alternatively, copper or stainless steel that iscoated with carbon, nickel, titanium, or the like can be used to formthe current collector. Alternatively, the positive electrode currentcollector 501 can be formed using an aluminum alloy to which an elementwhich improves heat resistance, such as silicon, neodymium, scandium, ormolybdenum, is added. The positive electrode current collector 501 canhave any of various shapes including a foil-like shape, a plate-likeshape (sheet-like shape), a net-like shape, a cylindrical shape, a coilshape, a punching-metal shape, an expanded-metal shape, a porous shape,and a shape of non-woven fabric as appropriate. The positive electrodecurrent collector 501 may be formed to have micro irregularities on thesurface thereof in order to enhance adhesion to the active materiallayer. The positive electrode current collector 501 preferably have athickness of more than or equal to 5 μm and less than or equal to 30 μm.

The positive electrode active material layer 502 includes a positiveelectrode active material. As described above, an “active material”refers only to a material that relates to insertion and extraction ofions functioning as carriers. In this specification and the like,however, a layer including a conductive additive, a binder, or the likeas well as a material that is actually a “active material” is alsoreferred to as an active material layer.

As the positive electrode active material, a material into and fromwhich lithium ions can be inserted and extracted can be used; forexample, a material having an olivine crystal structure, a layeredrock-salt crystal structure, a spinel crystal structure, or a NASICONcrystal structure, or the like can be used.

As the positive electrode active material, a compound such as LiFeO₂,LiCoO₂, LiNiO₂, of LiMn₂O₄, V₂O₅, Cr₂O₅, or MnO₂ can be used.

Further, lithium-containing complex phosphate (LiMPO₄ (general formula)(M is one or more of Fe(II), Mn(II), Co(II), and Ni(II))) can be used.Typical examples of LiMPO₄ are lithium metal phosphate compounds such asLiFePO₄, LiNiPO₄, LiCoPO₄, LiMnPO₄, LiFe_(a)Ni_(b)PO₄,LiFe_(a)Co_(b)PO₄, LiFe_(a)Mn_(b)PO₄, LiNi_(a)Co_(b)PO₄,LiNi_(a)Mn_(b)PO₄ (a+b≤1, 0<a<1, and 0<b<1), LiFe_(c)Ni_(d)Co_(e)PO₄,LiFe_(c)Ni_(d)Mn_(e)PO₄, LiNi_(c)Co_(d)Mn_(e)PO₄ (c+d+e≤1, 0<c<1, 0<d<1,and 0<e<1), and LiFe_(f)Ni_(g)Co_(h)Mn_(i)PO₄ (f+g+h+i≤1, 0<f<1, 0<g<1,0<h<1, and 0<i<1).

Further, a lithium-containing complex silicate such as Li(_(2-j))MSiO₄(general formula) (M is one or more of Fe(II), Mn(II), Co(II), andNi(II) and 0≤j≤2) can be used. Typical examples of Li(_(2-j))MSiO₄(general formula) are lithium silicate compounds such asLi(_(2-j))FeSiO₄, Li(_(2-j))NiSiO₄, Li(_(2-j))CoSiO₄, Li(_(2-j))MnSiO₄,Li(_(2-j))Fe_(k)Ni_(l)SiO₄, Li(_(2-j))Fe_(k)Co_(l)SiO₄,Li(_(2-j))Fe_(k)Mn_(l)SiO₄, Li(_(2-j))Ni_(k)Co_(l)SiO₄,Li(_(2-j))Ni_(k)Mn_(l)SiO₄ (k+l≤1, 0<k<1, and 0<l<1),Li(_(2-j))Fe_(m)Ni_(n)Co_(q)SiO₄, Li(_(2-j))Fe_(m)Ni_(n)Mn_(q)SiO₄,Li(_(2-j))Ni_(m)Co_(n)Mn_(q)SiO₄ (m+n+q≤1, 0<m<1, 0<n<1, and 0<q<1), andLi(_(2-j))Fe_(r)Ni_(s)Co_(t)Mn_(u)SiO₄ (r+s+t+u≤1, 0<r<1, 0<s<1, 0<t<1,and 0<u<1).

Still alternatively, a NASICON compound represented by a generalformula, A_(x)M₂(XO₄)₃ (A is Li, Na, or Mg, M is Fe, Mn, Ti, V, Nb, orAl, and X is S, P, Mo, W, As, or Si), can be used as the positiveelectrode active material. Examples of the NASICON compound areFe₂(MnO₄)₃, Fe₂(SO₄)₃, and Li₃Fe₂(PO₄)₃. Further alternatively, acompound expressed, by Li₂MPO₄F, Li₂MP₂O₇, or Li₅MO₄ (general formula)(M=Fe or Mn), a perovskite fluoride such as NaF₃ and FeF₃, a metalchalcogenide (a sulfide, a selenide, or a telluride) such as TiS₂ andMoS₂, a material with an inverse spinel structure such as LiMVO₄, avanadium oxide (V₂O₅, V₆O₁₃, LiV₃O₈, or the like), a manganese oxide, anorganic sulfur compound, or the like can be used as the positiveelectrode active material.

In the case where carrier ions are alkali metal ions other than lithiumions, or alkaline-earth metal ions, a compound containing carriers suchas an alkali metal (e.g., sodium and potassium) or an alkaline-earthmetal (e.g., calcium, strontium, barium, beryllium, and magnesium)instead of lithium of the lithium compound, the lithium-containingcomplex phosphate, or the lithium-containing complex silicate may beused as the positive electrode active material.

The average particle size of the positive electrode active material ispreferably, for example, larger than or equal to 5 nm and smaller thanor equal to 50 μm.

For example, lithium-containing complex phosphate having an olivinecrystal structure used for the positive electrode active material has aone-dimensional lithium diffusion path, so that lithium diffusion isslow. The average particle size of the active material is thuspreferably, for example, larger than or equal to 5 nm and smaller thanor equal to 1 μm in order to increase speed of charging and discharging.The specific surface area of the active material is, for example,preferably greater than or equal to 10 m²/g and less than or equal to 50m²/g.

A positive electrode active material having an olivine crystal structureis much less likely to be changed in the crystal structure by charge anddischarge and has a more stable crystal structure than, for example, anactive material having a layered rock-salt crystal structure. Thus, apositive electrode active material having an olivine crystal structureis stable toward operation such as overcharge. The use of such apositive electrode active material allows fabrication of a highly safepower storage device.

The positive electrode active material layer 502 may include aconductive additive. As the conductive additive, any of the materialsshown in the description of the structure of the negative electrode inEmbodiment 1 can be used, for example.

The positive electrode active material layer 502 may include a binder.As the binder, any of the materials shown in the description of thestructure of the negative electrode in Embodiment 1 can be used, forexample.

Here, the positive electrode active material layer 502 may containgraphene. Graphene is capable of making low-resistance surface contactand has extremely high conductivity even with a small thickness.Therefore, even a small amount of graphene can efficiently form aconductive path in an active material layer.

Here, for example, lithium-containing complex phosphate with an olivinecrystal structure used for the positive electrode active material has aone-dimensional lithium diffusion path, so that lithium diffusion isslow. The average size of particles of the active material is thus, forexample, preferably greater than or equal to 5 nm and less than or equalto 1 μm so that the charge and discharge rate is increased. The specificsurface area of the active material is, for example, preferably greaterthan or equal to 10 m²/g and less than or equal to 50 m²/g.

In the case where such an active material with a small average particlesize (e.g., 1 μm or less) is used, the specific surface area of theactive material is large and thus more conductive paths for the activematerial particles are needed. In such a case, it is particularlypreferred that graphene with extremely high conductivity that canefficiently form a conductive path even in a small amount be used.

FIG. 4 is a longitudinal cross-sectional view of the positive electrodeactive material layer 502 in the case of using graphene as theconductive additive. The positive electrode active material layer 502includes positive electrode active material particles 522, grapheneflakes 521 as the conductive additive, and the binder (not illustratedin the drawing).

The longitudinal section of the positive electrode active material layer502 in FIG. 4 shows substantially uniform dispersion of the grapheneflakes 521 in the positive electrode active material layer 502. Thegraphene flakes 521 are schematically shown by thick lines in FIG. 4 butare actually thin films each having a thickness corresponding to thethickness of a single layer or a multi-layer of carbon molecules. Theplurality of graphene flakes 521 are formed in such a way as to wrap,coat, or adhere to the surfaces of the plurality of positive electrodeactive material particles 522, so that the graphene flakes 521 makesurface contact with the positive electrode active material particles522. Furthermore, the graphene flakes 521 are also in surface contactwith each other; consequently, the plurality of graphene flakes 521 forma three-dimensional network for electric conduction.

This is because graphene oxide with extremely high dispersibility in apolar solvent is used for the formation of the graphene flakes 521. Thesolvent is removed by volatilization from a dispersion medium in whichgraphene oxide is uniformly dispensed, and the graphene oxide is reducedto graphene; hence, the graphene flakes 521 remaining in the positiveelectrode active material layer 502 partly overlap with each other andare dispersed such that surface contact is made, thereby forming anelectrical conduction path.

Unlike a conventional conductive additive in the form of particles, suchas acetylene black, which makes point contact with an active material,the graphene flake 521 is capable of making low-resistance surfacecontact; accordingly, the electrical conduction between the positiveelectrode active material particles 522 and the graphene flakes 521 canbe improved without an increase in the amount of a conductive additive.Thus, the proportion of the positive electrode active material particles522 in the positive electrode active material layer 502 can beincreased. Accordingly, the discharge capacity of a storage battery canbe increased.

[Formation Method of Positive Electrode]

Next, a method for forming the positive electrode 503 will be described.

The positive electrode 503 can be formed in a way similar to that offorming the negative electrode shown in Embodiment 2. For example, asolvent is added to the active material, the conductive additive, thebinder, and the like and they are mixed to make slurry, and then theslurry is applied and the solvent is volatilized, so that the positiveelectrode 503 is formed.

Note that the positive electrode active material layer 502 may be formedover only one surface of the positive electrode current collector 501,or the positive electrode active material layers 502 may be formed suchthat the positive electrode current collector 501 is sandwichedtherebetween. Alternatively, the positive electrode active materiallayers 502 may be formed such that part of the positive electrodecurrent collector is sandwiched therebetween.

The positive electrode current collector 501 may be subjected to surfacetreatment. Examples of such surface treatment are corona dischargetreatment, plasma treatment, and undercoat treatment. The surfacetreatment increases the wettability of the positive electrode currentcollector 501 to the positive electrode paste. In addition, the adhesionbetween the positive electrode current collector 501 and the positiveelectrode active material layer 502 can be increased.

After volatilization of the solvent, the obtained positive electrodeactive material layer 502 may be pressed by a compression method such asa roll press method or a flat plate press method so as to beconsolidated.

The thickness of the positive electrode active material layer 502 formedin the above-described manner is preferably greater than or equal to 5μm and less than or equal to 300 μm, more preferably greater than orequal to 10 μm and less than or equal to 150 μm, for example. The amountof the active material in the positive electrode active material layer502 is preferably greater than or equal to 2 mg/cm² and less than orequal to 50 mg/cm², for example.

Next, an example of a method for forming the positive electrode in whichgraphene is used as the conductive additive is described. First, theactive material, the binder, and graphene oxide are prepared. Though theexample of forming the positive electrode is shown here, the negativeelectrode shown in Embodiment 2 can be made in the same manner with theuse of graphene as the conductive additive, for example.

The graphene oxide is a raw material of the graphene flakes 521 thatserves as a conductive additive later. Graphene oxide can be formed byvarious synthesis methods such as a Hummers method, a modified Hummersmethod, and oxidation of graphite. Note that a method for forming astorage battery electrode of the present invention is not limited by thedegree of separation of graphene oxide.

For example, the Hummers method is a method for forming graphite oxideby oxidizing graphite such as flake graphite. The obtained graphiteoxide is graphite which is oxidized in places and thus to which afunctional group such as a carbonyl group, a carboxyl group, or ahydroxyl group is bonded. In the graphite oxide, the crystallinity ofthe graphite is lost and the distance between layers is increased.Therefore, the layers can be easily separated by ultrasonic treatment orthe like to obtain graphene oxide.

The length of one side (also referred to as a flake size) of thegraphene oxide is greater than or equal to 50 nm and less than or equalto 100 μm, preferably greater than or equal to 800 nm and less than orequal to 20 μm. Particularly, in the case where the flake size issmaller than the average particle size of the positive electrode activematerial particles 522, the surface contact with a plurality of thepositive electrode active material particles 522 and connection betweengraphene flakes become difficult, resulting in difficulty in improvingthe electrical conductivity of the positive electrode active materiallayer 502.

A solvent is added to the graphene oxide, the active material, and thebinder, and mixing is performed. As the solvent, water or a polarorganic solvent such as N-methylpyrrolidone (NMP) or dimethylformamidecan be used.

Note that graphene oxide may be contained at a proportion higher than orequal to 0.1 weight % and lower than or equal to 10 weight %, preferablyhigher than or equal to 0.1 weight % and lower than or equal to 5 weight%, further preferably higher than or equal to 0.2 weight % and lowerthan or equal to 1 weight % of the total weight of the mixture of thegraphene oxide, the positive electrode active material, the conductiveadditive, and the binder. On the other hand, the graphene obtained afterthe positive electrode paste is applied to the current collector andreduction is performed may be contained at a proportion higher than orequal to 0.05 weight % and lower than or equal to 5 weight %, preferablyhigher than or equal to 0.05 weight % and lower than or equal to 2.5weight %, further preferably higher than or equal to 0.1 weight % andlower than or equal to 0.5 weight % of the total weight of the positiveelectrode active material layer. This is because the weight of thegraphene is reduced by almost half due to the reduction of the grapheneoxide.

Note that a solvent may be further added after the mixing so that theviscosity of the mixture can be adjusted. The mixing and the addition ofthe polar solvent may be repeated plural times. By the above steps, theslurry to be applied to the electrode is obtained.

Next, the obtained slurry is applied onto a current collector.

Then, the solvent is volatilized from the slurry applied to the positiveelectrode current collector 501 by a method such as ventilation dryingor reduced pressure (vacuum) drying. whereby the positive electrodeactive material layer 502 is formed. The volatilization of the solventis preferably performed using, for example, a hot wind at a temperaturehigher than or equal to 50° C. and lower than or equal to 160° C., Thereis no particular limitation on the atmosphere.

Next, reduction of the graphene oxide is preferably performed. Thereduction is performed by heat treatment or with the use of a reducingagent, for example.

An example of a reducing method using a reducing agent will be describedbelow. First, a reaction is caused in a solvent containing a reducingagent. Through this step, the graphene oxide contained in the activematerial layer is reduced to form the graphene flakes 521. Note thatoxygen in the graphene oxide is not necessarily entirely released andpossibly remains in the graphene partly. When graphene flakes 521contains oxygen, the ratio of oxygen measured by XPS in graphene ishigher than or equal to 2 atomic % and lower than or equal to 20 atomic%, preferably higher than or equal to 3 atomic % and lower than or equalto 15 atomic %. This reduction treatment is preferably performed athigher than or equal to room temperature and lower than or equal to 150°C.

Examples of the reducing agent are ascorbic acid, hydrazine, dimethyl,hydrazine, hydroquinone, sodium boron hydride (NaBH₄), tetra butylammonium bromide (TBAB), LiAlH₄, ethylene glycol, polyethylene glycol,N,N-diethylhydroxylamine, and a derivative thereof.

A polar solvent can be used as the solvent. Any material can be used forthe polar solvent as long as it can dissolve the reducing agent.Examples of the material of the polar solvent are water, methanol,ethanol, acetone, tetrahydrofuran (THF), dimethylformamide (DMF),N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and a mixedsolution of any two or more of the above.

After that, washing and drying are performed to volatilize the solvent.The solvent is preferably volatilized under a reduced pressure (invacuum) or in a reduction atmosphere. The volatilization step of thesolvent is preferably performed, for example, in vacuum at a temperaturehigher than or equal to 50° C. and lower than or equal to 160° C. forlonger than or equal to 10 minutes and shorter than or equal to 48hours. The treatment allows evaporation, volatilization, or removal ofthe polar solvent and moisture in the positive electrode active materiallayer 502. The volatilization of the solvent may be followed bypressing.

Alternatively, the solvent may be volatilized using a drying furnace orthe like. In the case of using a drying furnace, the heat treatment isperformed at 30° C. or higher and 200° C. or lower for longer than orequal to 30 seconds and shorter than or equal to 20 minutes, forexample. The temperature may be increased in stages.

Note that heating can facilitate the reduction reaction caused using thereducing agent. After volatilization of the solvent following thechemical reduction, heating may further be performed.

In the case of not performing reduction with the use of a reducingagent, reduction can be performed by heat treatment. For example,reduction by heat treatment can be performed under a reduced pressure(in vacuum) at a temperature higher than or equal to 150° C. for longerthan or equal to 0.5 hours and shorter than or equal to 30 hours.

Through the above steps, the positive electrode active material layer502 in which the positive electrode active material particles 522 andthe graphene flakes 521 are uniformly dispersed can be formed.

Here, reduction is preferably performed on an electrode using grapheneoxide. It is more preferred that reduction be performed in such a mannerthat chemical reduction and thermal reduction are performed in thisorder. In thermal reduction, oxygen atoms are released in the form of,for example, carbon dioxide. In contrast, in chemical reduction,reduction is performed using a chemical reaction, whereby the proportionof carbon atoms that form an sp² bond of graphene can be high.Furthermore, thermal reduction is preferably performed after chemicalreduction, in which case the conductivity of formed graphene can befurther increased.

As a solvent of the electrolytic solution 508, an aprotic organicsolvent is preferably used. For example, one of ethylene carbonate (EC),propylene carbonate (PC), butylene carbonate, chloroethylene carbonate,vinylene carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate(DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methylformate, methyl acetate, methyl butyrate, 1,3-dioxane, 1,4-dioxane,dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyldiglyme, acetonitrile, benzonitrile, tetrahydrofuran, sulfolane, andsultone can be used, or two or more of these solvents can be used in anappropriate combination in an appropriate ratio.

When a gelled high-molecular material is used as the solvent for theelectrolytic solution, safety against liquid leakage and the like isimproved. Further, a secondary battery can be thinner and morelightweight. Typical examples of the gelled high-molecular materialinclude a silicone gel, an acrylic gel, an acrylonitrile gel, apoly(ethylene oxide)-based gel, a poly(propylene oxide)-based gel, a gelof a fluorine-based polymer, and the like.

Alternatively, the use of one or more of ionic liquids (room temperaturemolten salts) which are less likely to burn and volatilize as thesolvent for the electrolytic solution can prevent the power storagedevice from exploding or catching fire even when the power storagedevice internally shorts out or the internal temperature increases dueto overcharging or the like. An ionic liquid is composed of a cation andan anion, and includes an organic cation and an anion. Examples of theorganic cation used for the electrolytic solution are aliphatic oniumcations, such as a quaternary ammonium cation, a tertiary sulfoniumcation, and a quaternary phosphonium cation, and aromatic cations, suchas an imidazolium cation and a pyridinium cation. Examples of the anionused for the electrolytic solution include a monovalent amide-basedanion, a monovalent methide-based anion, a fluorosulfonate anion, aperfluoroalkylsulfonate anion, tetrafluoroborate, perfluoroalkylborate,hexafluorophosphate, and perfluoroalkylphosphate.

In the case of using a lithium ion as a carrier ion, as an electrolytedissolved in the above-described solvent, one of lithium salts such asLiPF₆, LiClO₄, LiAsF₆, LiBF₄, LiAlCl₄, LiSCN, LiBr, LiI, Li₂SO₄,Li₂B₁₀Cl₁₀, Li₂B₁₂Cl₁₂, LiCF₃SO₃, LiC₄F₉SO₃, LiC(CF₃SO₂)₃,LiC(C₂F₅SO₂)₃, LiN(CF₃SO₂)₂, LiN(C₄F₉SO₂) (CF₃SO₂), and LiN(C₂F₅SO₂)₂can be used, or two or more of these lithium salts can be used in anappropriate combination in an appropriate ratio.

The electrolytic solution used for the power storage device ispreferably a highly purified one so as to contain a negligible amount ofdust particles and elements other than the constituent elements of theelectrolytic solution (hereinafter, also simply referred to asimpurities). Specifically, the proportion of the weight of impurities tothe electrolytic solution is less than or equal to 1%, preferably lessthan or equal to 0.1%, and more preferably less than or equal to 0.01%.

Furthermore, an additive agent such as vinylene carbonate, propanesulfone (PS), tert-butylbenzene (TBB), fluoroethylene carbonate (FEC),or LiBOB may be added to the electrolytic solution. The concentration ofsuch an additive agent in the whole solvent is, for example, higher thanor equal to 0.1 wt % and lower than or equal to 5 wt %.

Alternatively, a gelled electrolyte obtained in such a manner that apolymer is swelled with an electrolytic solution may be used. Examplesof the gelled electrolyte (polymer-gel electrolyte) include a hostpolymer which is used as a support and contains the electrolyticsolution described above.

Examples of the host polymer are explained below. Examples of the hostpolymer include a polymer having a polyalkylene oxide structure, such aspolyethylene oxide (PEO); PVDF; polyacrylonitrile; and a copolymercontaining any of them. For example, PVDF-HFP, which is a copolymer ofPVDF and hexafluoropropylene (HFP) can be used. The formed polymer maybe porous.

Instead of the electrolytic solution, a solid electrolyte including aninorganic material such as a sulfide-based inorganic material or anoxide-based inorganic material, or a solid electrolyte including amacromolecular material such as a polyethylene oxide (PEO)-basedmacromolecular material may alternatively be used. In the case of usingthe solid electrolyte, a separator or a spacer is not necessary.Further, the battery can be entirely solidified; therefore, there is nopossibility of liquid leakage and thus the safety of the battery isdramatically increased.

As the separator 507, paper; nonwoven fabric; glass fiber; ceramics;synthetic fiber containing nylon (polyamide), vinylon (polyvinylalcohol-based fiber), polyester, acrylic, polyolefin, or polyurethane;or the like can be used.

[Fabricating Method of Thin Storage Battery]

A method for fabricating the storage battery is described below. Theseparator 507 is preferably formed to have a bag-like shape to surroundone of the positive electrode 503 and the negative electrode 506. Forexample, as illustrated in FIG. 7A, the separator 507 is folded in twosuch that the positive electrode 503 is sandwiched, and sealed with asealing member 514 in a region outside the region overlapping with thepositive electrode 503; thus, the positive electrode 503 can be surelysurrounded by the separator 507. Then, as illustrated in FIG. 7B, thepositive electrodes 503 surrounded by the separators 507 and thenegative electrodes 506 are alternately stacked and provided in theexterior body 509, whereby the thin storage battery 500 can be formed.

FIG. 8B illustrates an example in which a current collector is welded toa lead electrode, specifically, an example where positive electrodecurrent collectors 501 are welded to a positive electrode lead electrode510. The positive electrode current collectors 501 are welded to thepositive electrode lead electrode 510 in a welding region 512 byultrasonic welding or the like. The positive electrode current collector501 includes a bent portion 513 as illustrated in FIG. 8B, and it istherefore possible to relieve stress due to external force applied alterfabrication of the storage battery 500. The reliability of the storagebattery 500 can be thus increased.

In the thin storage battery 500 illustrated in FIGS. 7A and 7B and FIGS.8A and 8B, the positive electrode current collectors 501 and thenegative electrode current collectors 504 are welded to the positiveelectrode lead electrode 510 and a negative electrode lead electrode511, respectively, by ultrasonic welding such that part of the positiveelectrode lead electrode 510 and part of the negative electrode leadelectrode 511 are exposed to the outside. The positive electrode currentcollector 501 and the negative electrode current collector 504 candouble as terminals for electrical contact with the outside. In thatcase, the positive electrode current collector 501 and the negativeelectrode current collector 504 may be arranged such that part of thepositive electrode current collector 501 and part of the negativeelectrode current collector 504 are exposed to the outside the exteriorbody 509 without using leading electrodes.

Although the positive electrode lead electrode 510 and the negativeelectrode lead electrode 511 are provided on the same side in FIGS. 7Aand 7B, the positive electrode lead electrode 510 and the negativeelectrode lead electrode 511 may be provided on different sides asillustrated in FIG. 9. The lead electrodes of a storage battery of oneembodiment of the present invention can be freely positioned asdescribed above; therefore, the degree of freedom in design is high.Accordingly, a product including a storage battery of one embodiment ofthe present invention can have a high degree of freedom in design.Furthermore, production efficiency of products each including a storagebattery of one embodiment of the present invention can be increased.

As the exterior body 509 in the thin storage battery 500, for example, afilm having a three-layer structure in which a highly flexible metalthin film of aluminum, stainless steel, copper, nickel, or the like isprovided over a film formed of a material such as polyethylene,polypropylene, polycarbonate, ionomer, or polyamide, and an insulatingsynthetic resin film of a polyamide-based resin, a polyester-basedresin, or the like is provided as the outer surface of the exterior bodyover the metal thin film can be used.

In FIGS. 6A and 6B and FIG. 7B, five pairs of a positive electrode and anegative electrode facing each other are illustrated as an example.Needless to say, the number of a pair of electrodes facing each other isnot limited to 5 and may be more than 5 or less than 5. In the case of alarge number of electrode layers, the storage battery can have highcapacity. In contrast, in the case of a small number of electrodelayers, the storage battery can have small thickness and highflexibility.

In the above structure, the exterior body 509 of the secondary batterycan change its form with a radius of curvature greater than or equal to30 mm, preferably greater than or equal to 10 mm. The exterior body ofthe secondary battery is formed of one or two films. In the case of thesecondary battery having a layered structure, a cross-sectionalstructure of the battery that is bent is surrounded by two curves of thefilm serving as the exterior body.

A description is given of the radius of curvature of a surface withreference to FIGS. 10A to 10C. In FIG. 10A, on a plane 1701 along whicha curved surface 1700 is cut, part of a curve 1702, which is a form ofthe curved surface, is approximate to an arc of a circle, and the radiusof the circle is referred to as a radius 1703 of curvature and thecenter of the circle is referred to as a center 1704 of curvature. FIG.10B is a top view of the curved surface 1700. FIG. 10C is across-sectional view of the curved surface 1700 taken along the plane1701. When a curved surface is cut along a plane, the radius ofcurvature of a curve in a cross section differs depending on the anglebetween the curved surface and the plane or on the cut position, and thesmallest radius of curvature is defined as the radius of curvature of asurface in this specification and the like.

In the case of curving a secondary battery in which a component 1805including electrodes and an electrolytic solution is sandwiched betweentwo films as exterior bodies, a radius 1802 of curvature of a film 1801close to a center 1800 of curvature of the secondary battery is smallerthan a radius 1804 of curvature of a film 1803 far from the center 1800of curvature (FIG. 11A). When the secondary battery is curved and has anarc-shaped cross section, compressive stress is applied to a surface ofthe film close to the center 1800 of curvature and tensile stress isapplied to a surface of the film far from the center 1800 of curvature(FIG. 11B). However, by forming a pattern of projections and depressionson surfaces of the exterior bodies, influence of distortion can bereduced to be acceptable even when the compressive stress and thetensile stress are applied. For this reason, the secondary battery canchange its form such that the exterior body on the side closer to thecenter of curvature has a curvature radius greater than or equal to 30mm, preferably greater than or equal to 10 mm.

Note that the cross-sectional shape of the secondary battery is notlimited to a simple arc shape, and the cross section can be partlyarc-shaped; for example, a shape illustrated in FIG. 11C, a wavy shapeillustrated in FIG. 11D, or an S shape can be used. When the curvedsurface of the secondary battery has a shape with a plurality of centersof curvature, the secondary battery can change its form such that acurved surface with the smallest radius of curvature among radii ofcurvature with respect to the plurality of centers of curvature, whichis a surface of the exterior body on the side closer to the center ofcurvature, has a curvature radius greater than or equal to 30 mm,preferably greater than or equal to 10 mm.

Next, aging after fabrication of a storage battery will be described.Aging is preferably performed after fabrication of a storage battery.The aging can be performed under the following conditions, for example.Charge is performed at a rate of 0.001 C or more and 0.2 C or less of atemperature higher than or equal to room temperature and lower than orequal to 50° C. In the case where an electrolytic solution is decomposedand a gas is generated and accumulated in the cell, the electrolyticsolution cannot be in contact with a surface of the electrode in someregions. That is to say, an effectual reaction area of the electrode isreduced and effectual current density is increase.

When the current density is extremely high, a voltage drop occursdepending on the resistance of the electrode, lithium is inserted intothe active material and lithium is deposited on the surface of theactive material. The lithium deposition might reduce capacity. Forexample, if a coating film or the like is grown on the surface afterlithium deposition, lithium deposited on the surface cannot be dissolvedagain. This lithium cannot contribute to capacity. In addition, whendeposited lithium is physically collapsed and conduction with theelectrode is lost, the lithium also cannot contribute to capacity.Therefore, the gas is preferably released before the potential of theelectrode reaches the potential of lithium because of a voltage drop.

After the release of the gas, the charging state may be maintained at atemperature higher than room temperature, preferably higher than orequal to 30° C. and lower than or equal to 60° C., more preferablyhigher than or equal to 35° C. and lower than or equal to 50° C. for,for example, 1 hour or more and 100 hours or less. In the initialcharge, an electrolytic solution decomposed on the surface forms acoating film. The formed coating film may thus be densified when thecharging state is held at a temperature higher than room temperatureafter the release of the gas, for example.

[Coin-type Storage Battery]

Next, an example of a coin-type storage battery will be described as anexample of a power storage device with reference to FIGS. 12A and 12B.FIG. 12A is an external view of a coin-type (single-layer flat type)storage battery, and FIG. 12B is a cross-sectional view thereof.

In a coin-type storage battery 300, a positive electrode can 301doubling as a positive electrode terminal and a negative electrode can302 doubling as a negative electrode terminal are insulated from eachother and scaled by a gasket 303 made of polypropylene or the like. Anegative electrode 307 includes a negative electrode current collector308 and a negative electrode active material layer 309 provided incontact with the negative electrode current collector 308. The negativeelectrode active material layer 309 includes the negative electrodeactive material shown in Embodiment 1. For the negative electrode 307,the negative electrode shown in Embodiment 2 is preferably used.

A positive electrode 304 includes a positive electrode current collector305 and a positive electrode active material layer 306 provided incontact with the positive electrode current collector 305. Thedescription of the positive electrode active material layer 502 can bereferred to for the positive electrode active material layer 306. Thedescription of the separator 507 can be referred to for the separator310. The description of the electrolytic solution 508 can be referred tofor the electrolytic solution.

Note that only one surface of each of the positive electrode 304 and thenegative electrode 307 used for the coin-type storage battery 300 isprovided with an active material layer.

For the positive electrode can 301 and the negative electrode can 302, ametal having corrosion resistance to an electrolytic solution, such asnickel, aluminum, or titanium, an alloy of such metals, or an alloy ofsuch a metal and another metal (stainless or the like) can be used.Alternatively, it is preferable to cover the positive electrode can 301and the negative electrode can 302 with nickel, aluminum, or the like inorder to prevent corrosion due to the electrolytic solution. Thepositive electrode can 301 and the negative electrode can 302 areelectrically connected to the positive electrode 304 and the negativeelectrode 307 respectively.

The negative electrode 307, the positive electrode 304, and theseparator 310 are soaked in the electrolytic solution. Then, asillustrated in FIG. 12B, the positive electrode 304, the separator 310,the negative electrode 307, and the negative electrode can 302 arestacked in this order with the positive electrode can 301 positioned atthe bottom, and the positive electrode can 301 and the negativeelectrode can 302 are subjected to pressure bonding with the gasket 303provided therebetween. In such a manner, the coin-type storage battery300 can be fabricated.

[Cylindrical Storage Battery]

Next, an example of a cylindrical storage battery will be described asan example of a power storage device. The cylindrical storage batterywill be described with reference to FIGS. 13A and 13B. As illustrated inFIG. 13A, a cylindrical storage battery 600 includes a positiveelectrode cap (battery cap) 601 on the top surface and a battery can(outer can) 602 on the side surface and bottom surface. The positiveelectrode cap 601 and the battery can (outer can) 602 are insulated fromeach other by a gasket (insulating gasket) 610.

FIG. 13B is a schematic view of a cross-section of the cylindricalstorage battery. Inside the battery can 602 having a hollow cylindricalshape, a battery element in which a strip-like positive electrode 604and a strip-like negative electrode 606 are wound with a stripe-likeseparator 605 provided therebetween is provided. Although notillustrated, the battery element is wound around a center pin. One endof the battery can 602 is close and the other end thereof is open. Forthe battery can 602, a metal having a corrosion-resistant property to anelectrolytic solution, such as nickel, aluminum, or titanium, an alloyof such a metal, or an alloy of such a metal and an another metal (e.g.,stainless steel or the like) can be used. Alternatively, it ispreferable to cover the battery can with nickel, aluminum, or the likein order to prevent corrosion due to the electrolytic solution. Insidethe battery can 602, the battery element in which the positiveelectrode, the negative electrode, and the separator are wound isprovided between a pair of insulating plates 608 and 609 which face eachother. Further, a nonaqueous electrolytic solution (not illustrated) isinjected inside the battery can 602 provided with the battery element.As the nonaqueous electrolytic solution, a nonaqueous electrolyticsolution which is similar to that of the above coin-type storage batterycan be used.

For the negative electrode 606, the negative electrode shown inEmbodiment 2 is preferably used. The positive electrode 604 can beformed in a way similar to that of forming the positive electrode 503 inthe above-described thin storage battery. Since the positive electrodeand the negative electrode of the cylindrical storage battery are wound,active materials are preferably formed on both sides of the currentcollectors. A positive electrode terminal (positive electrode currentcollecting lead) 603 is connected to the positive electrode 604, and anegative electrode terminal (negative electrode current collecting lead)607 is connected to the negative electrode 606. Both the positiveelectrode terminal 603 and the negative electrode terminal 607 can beformed using a metal material such as aluminum. The positive electrodeterminal 603 and the negative electrode terminal 607 areresistance-welded to a safety valve mechanism 612 and the bottom of thebattery can 602, respectively. The safety valve mechanism 612 iselectrically connected to the positive electrode cap 601 through apositive temperature coefficient (PTC) element 611. The safety valvemechanism 612 cuts off electrical connection between the positiveelectrode cap 601 and the positive electrode 604 when the internalpressure of the battery exceeds a predetermined threshold value.Further, the PTC element 611, which serves as a thermally sensitiveresistor whose resistance increases as temperature rises, limits theamount of current by increasing the resistance, in order to preventabnormal heat generation. Note that barium titanate (BaTiO₃)-basedsemiconductor ceramic or the like can be used for the PTC element.

Note that in this embodiment, the coin-type storage battery, thecylindrical storage battery, and the thin storage battery are given asexamples of the storage battery; however, any of storage batteries witha variety of shapes, such as a scaled storage battery and a rectangularstorage battery, can be used. Further, a structure in which a pluralityof positive electrodes, a plurality of negative electrodes, and aplurality of separators are stacked or rolled may be employed. Forexample, FIGS. 14A to 14C, FIGS. 15A to 15C, FIGS. 16A and 16B, FIGS.17A1 to 17B2, and FIGS. 18A and 18B illustrate examples of other storagebatteries.

[Structural Example of Storage Battery]

FIGS. 14A to 14C and FIGS. 15A to 15C illustrate structural examples ofthin storage batteries. A wound body 993 illustrated in FIG. 14Aincludes a negative electrode 994, a positive electrode 995, and aseparator 996.

The wound body 993 is obtained by winding a sheet of stacks in each ofwhich the negative electrode 994 overlaps with the positive electrode995 with the separator 996 provided therebetween. The wound body 993 iscovered with a rectangular sealed container or the like; thus, arectangular secondary battery is fabricated.

Note that the number of stacks each including the negative electrode994, the positive electrode 995, and the separator 996 may be determinedas appropriate depending on capacity and an element volume which arerequired. The negative electrode 994 is connected to a negativeelectrode current collector (not illustrated) via one of a leadelectrode 997 and a lead electrode 998. The positive electrode 995 isconnected to a positive electrode current collector (not illustrated)via the other of the lead electrode 997 and the lead electrode 998.

In a storage battery 980 illustrated in FIGS. 14B and 14C, the woundbody 993 is packed in a space formed by bonding a film 981 and a film982 having a depressed portion that serve as an exterior body bythermocompression bonding or the like. The wound body 993 includes thelead electrode 997 and the lead electrode 998, and is soaked in anelectrolytic solution inside a space surrounded by the film 981 and thefilm 982 having a depressed portion.

For the film 981 and the film 982 having a depressed portion, a metalmaterial such as aluminum or a resin material can be used, for example.With the use of a resin material for the film 981 and the film 982having a depressed portion, the film 981 and the film 982 having adepressed portion can be changed in their forms when external force isapplied; thus, a flexible storage battery can be fabricated.

Although FIGS. 14B and 14C illustrate an example where a space is formedby two films, the wound body 993 may be placed in a space formed bybending one film.

Furthermore, a flexible power storage device can be fabricated when aresin material or the like is used for the exterior body and the sealedcontainer of the power storage device. Note that in the case where aresin material is used for the exterior body and the sealed container, aconductive material is used for a portion connected to the outside.

For example, FIGS. 15A to 15C illustrate another example of a flexiblethin storage battery. The wound body 993 illustrated in FIG. 15A is thesame as that illustrated in FIG. 14A, and a detailed description thereofis omitted.

In a storage battery 990 illustrated in FIGS. 15B and 15C, the woundbody 993 is packed in an exterior body 991. The wound body 993 includesthe lead electrode 997 and the lead electrode 998, and is soaked in anelectrolytic solution inside a space surrounded by the exterior body 991and an exterior body 992. For example, a metal material such as aluminumor a resin material can be used for the exterior bodies 991 and 992.With the use of a resin material for the exterior bodies 991 and 992,the exterior bodies 991 and 992 can be changed in their forms whenexternal force is applied; thus, a flexible thin storage battery can befabricated.

[Structural Example of Power Storage System]

Structural examples of power storage systems will be described withreference to FIGS. 16A and 16B, FIGS. 17A1 to 17B2, and FIGS. 18A and18B. Here, a power storage system refers to, for example, a deviceincluding a power storage device.

FIGS. 16A and 16B show external views of a power storage system. Thepower storage system includes a circuit board 900 and a storage battery913. A label 910 is attached to the storage battery 913. As shown inFIG. 16B, the power storage system further includes a terminal 951, aterminal 952, an antenna 914, and an antenna 915.

The circuit board 900 includes terminals 911 and a circuit 912. Theterminals 911 are connected to the terminals 951 and 952, the antennas914 and 915, and the circuit 912. Note that a plurality of terminals 911serving as a control signal input terminal, a power supply terminal, andthe like may be provided.

The circuit 912 may be provided on the rear side of the circuit board900. Each of the antennas 914 and 915 is not limited to having a coilshape and may have a linear shape or a plate shape. Further, a planarantenna, an aperture antenna, a traveling-wave antenna, an EH antenna, amagnetic-field antenna, a dielectric antenna, or the like may be used.Alternatively, the antenna 914 or the antenna 915 may be a flat-plateconductor. The flat-plate conductor can serve as one of conductors forelectric field coupling. That is, the antenna 914 or the antenna 915 canserve as one of two conductors of a capacitor. Thus, power can betransmitted and received not only by an electromagnetic field or amagnetic field but also by an electric field.

The line width of the antenna 914 is preferably larger than that of theantenna 915. This makes it possible to increase the amount of electricpower received by the antenna 914.

The power storage system includes a layer 916 between the storagebattery 913 and the antennas 914 and 915. The layer 916 has a functionof blocking an electromagnetic field from the storage battery 913, forexample. As the layer 916, for example, a magnetic body can be used.

Note that the structure of the power storage system is not limited tothat shown in FIGS. 16A and 16B.

For example, as shown in FIGS. 17A1 and 17A2, two opposing surfaces ofthe storage battery 913 in FIGS. 16A and 16B may be provided withrespective antennas. FIG. 17A1 is an external view illustrating one ofthe opposing surfaces, and FIG. 17A2 is an external view illustratingthe other of the opposing surfaces. Note that for the same portions asthe power storage system in FIGS. 16A and 16B, description on the powerstorage system in FIGS. 16A and 16B can be referred to as appropriate.

As illustrated in FIG. 17A1, the antenna 914 is provided on one of theopposing surfaces of the storage battery 913 with the layer 916 providedtherebetween, and as illustrated in FIG. 17A2, an antenna 915 isprovided on the other of the opposing surfaces of the storage battery913 with the layer 917 provided therebetween. The layer 917 has afunction of blocking an electromagnetic field from the storage battery913, for example. As the layer 917, for example, a magnetic body can beused.

With the above structure, both of the antennas 914 and 915 can beincreased in size.

Alternatively, as illustrated in FIGS. 17B1 and 17B2, two opposingsurfaces of the storage battery 913 in FIGS. 16A and 16B may be providedwith different types of antennas. FIG. 17B1 is an external view showingone of the opposing surfaces, and FIG. 17B2 is an external view showingthe other of the opposing surfaces. Note that for the same portions asthe power storage system in FIGS. 16A and 16B, description on the powerstorage system in FIGS. 16A and 16B can be referred to as appropriate.

As illustrated in FIG. 17B1, the antenna 914 and the antenna 915 areprovided on one of the opposing surfaces of the storage battery 913 withthe layer 916 provided therebetween, and as illustrated in FIG. 17B2, anantenna 918 is provided on the other of the opposing surfaces of thestorage battery 913 with a layer 917 provided therebetween. The antenna918 has a function of performing data communication with an externaldevice, for example. An antenna with a shape that can be used for theantennas 914 and 915, for example, can be used as the antenna 918. As anexample of a method for communication between the power storage systemand another device via the antenna 918, a response method that can beused between the power storage system and another device, such as NFC,can be employed.

Alternatively, as illustrated in FIG. 18A, the storage battery 913 inFIGS. 16A and 16B may be provided with a display device 920. The displaydevice 920 is electrically connected to the terminal 911 via a terminal919. It is possible that the label 910 is not provided in a portionwhere the display device 920 is provided. Note that for the sameportions as the power storage system in FIGS. 16A and 16B, descriptionon the power storage system in FIGS. 16A and 16B can be referred to asappropriate.

The display device 920 can display, for example, an image showingwhether or not charging is being carried out, an image showing theamount of stored power, or the like. As the display device 920,electronic paper, a liquid crystal display device, an electroluminescent(EL) display device, or the like can be used. For example, powerconsumption of the display device 920 can be reduced when electronicpaper is used.

Alternatively, as illustrated in FIG. 18B, the storage battery 913illustrated in FIGS. 16A and 16B may be provided with a sensor 921. Thesensor 921 is electrically connected to the terminal 911 via a terminal922. Note that for the same portions as the power storage system inFIGS. 16A and 16B, description on the power storage system in FIGS. 16Aand 16B can be referred to as appropriate.

As the sensor 921, a sensor that has a function of measuring, forexample, force, displacement, position, speed, acceleration, angularvelocity, rotational frequency, distance, light, liquid, magnetism,temperature, chemical substance, sound, time, hardness, electric field,electric current, voltage, electric power, radiation, flow rate,humidity, gradient, oscillation, odor, or infrared rays can be used.With the sensor 921, for example, data on the environment (e.g.,temperature) where the power storage system is placed can be acquiredand stored in a memory in the circuit 912.

The electrode of one embodiment of the present invention is used in thestorage battery and the power storage system that are described in thisembodiment. The capacity of the storage battery and the power storagesystem can thus be high. Furthermore, energy density can be high.Moreover, reliability can be high, and life can be long,

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Embodiment 4

In this embodiment, an example of an electronic device including aflexible storage battery will be described.

FIGS. 19A to 19G illustrate examples of electronic devices including theflexible storage batteries described in Embodiment 2. Examples of anelectronic device including a flexible power storage device includetelevision devices (also referred to as televisions or televisionreceivers), monitors of computers or the like, cameras such as digitalcameras or digital video cameras, digital photo frames, mobile phones(also referred to as cellular phones or mobile phone devices), portablegame machines, portable information terminals, audio reproducingdevices, large game machines such as pachinko machines, and the like.

In addition, a flexible power storage device can be incorporated along acurved inside/outside wall surface of a house or a building or a curvedinterior/exterior surface of a car.

FIG. 19A illustrates an example of a mobile phone. A mobile phone 7400is provided with a display portion 7402 incorporated in a housing 7401,an operation button 7403, an external connection port 7404, a speaker7405, a microphone 7406, and the like. Note that the mobile phone 7400includes a power storage device 7407.

The mobile phone 7400 illustrated in FIG. 19B is bent. When the wholemobile phone 7400 is bent by the external force, the power storagedevice 7407 included in the mobile phone 7400 is also bent. FIG. 19Cillustrates the bent power storage device 7407. The power storage device7407 is a thin storage battery. The power storage device 7407 is fixedin a state of being bent. Note that the power storage device 7407includes a lead electrode electrically connected to a current collector.The current collector is, for example, copper foil, and partly alloyedwith gallium; thus, adhesion between the current collector and an activematerial layer in contact with the current collector is improved and thepower storage device 7407 can have high reliability even in a state ofbeing bent.

FIG. 19D illustrates an example of a bangle-type display device. Aportable display device 7100 includes a housing 7101, a display portion7102, an operation button 7103, and a power storage device 7104. FIG.19E illustrates the bent power storage device 7104. When the displaydevice is worn on a user's arm while the power storage device 7104 isbent, the housing changes its form and the curvature of a part or thewhole of the power storage device 7104 is changed. Note that the radiusof curvature of a curve at a point refers to the radius of the circulararc that best approximates the curve at that point. The reciprocal ofthe radius of curvature is curvature. Specifically, a part or the wholeof the housing or the main surface of the power storage device 7104 ischanged in the range of radius of curvature from 40 mm to 150 mm. Whenthe radius of curvature at the main surface of the power storage device7104 is greater than or equal to 40 mm and less than or equal to 150 mm,the reliability can be kept high.

FIG. 19F illustrates an example of a watch-type portable informationterminal. A portable information terminal 7200 includes a housing 7201,a display portion 7202, a band 7203, a buckle 7204, an operation button7205, an input output terminal 7206, and the like.

The portable information terminal 7200 is capable of executing a varietyof applications such as mobile phone calls, e-mailing, viewing andediting texts, music reproduction, Internet communication, and acomputer game.

The display surface of the display portion 7202 is bent, and images canbe displayed on the bent display surface. Further, the display portion7202 includes a touch sensor, and operation can be performed by touchingthe screen with a finger, a stylus, or the like. For example, bytouching an icon 7207 displayed on the display portion 7202, applicationcan be started.

With the operation button 7205, a variety of functions such as timesetting, power ON/OFF, ON/OFF of wireless communication, setting andcancellation of manner mode, and setting and cancellation of powersaving mode can be performed. For example, the functions of theoperation button 7205 can be set freely by the operating systemincorporated in the portable information terminal 7200.

Further, the portable information terminal 7200 can perform near fieldcommunication that is a communication method based on an existingcommunication standard. In that case, for example, mutual communicationbetween the portable information terminal 7200 and a headset capable ofwireless communication can be performed, and thus hands-free calling ispossible.

Moreover, the portable information terminal 7200 includes the inputoutput terminal 7206, and data can be directly transmitted to andreceived from another information terminal via a connector. Powercharging through the input output terminal 7206 is possible. Note thatthe charging operation may be performed by wireless power feedingwithout using the input output terminal 7206.

The display portion 7202 of the portable information terminal 7200 isprovided with a power storage device including the electrode member ofone embodiment of the present invention. For example, the power storagedevice 7104 illustrated in FIG. 19E that is in the state of being curvedcan be provided in the housing 7201. Alternatively, the power storagedevice 7104 illustrated in FIG. 19E can be provided in the band 7203such that it can be curved.

FIG. 19G illustrates an example of an armband-type display device. Adisplay device 7300 includes a display portion 7304 and the powerstorage device of one embodiment of the present invention. The displaydevice 7300 can include a touch sensor in the display portion 7304 andcan serve as a portable information terminal.

The display surface of the display portion 7304 is bent, and images canbe displayed on the bent display surface. A display state of the displaydevice 7300 can be changed by, for example, near field communicationthat is a communication method based on an existing communicationstandard.

The display device 7300 includes an input output terminal, and data canbe directly transmitted to and received from another informationterminal via a connector. Power charging through the input outputterminal is possible. Note that the charging operation may be performedby wireless power feeding without using the input output terminal.

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Embodiment 5

In this embodiment, examples of electronic devices that can includepower storage devices will be described.

FIGS. 20A and 20B illustrate an example of a tablet terminal that can befolded in half. A tablet terminal 9600 illustrated in FIGS. 20A and 20Bincludes a housing 9630 a, a housing 9630 b, a movable portion 9640connecting the housings 9630 a and 9630 b, a display portion 9631provided with a display portion 9631 a and a display portion 9631 b, adisplay mode switch 9626, a power switch 9627, a power saver switch9625, a fastener 9629, and an operation switch 9628. FIGS. 20A and 20Billustrate the tablet terminal 9600 opened and closed, respectively.

The tablet terminal 9600 includes a power storage unit 9635 inside thehousings 9630 a and 9630 b. The power storage unit 9635 is providedacross the housings 9630 a and 9630 b, passing through the movableportion 9640.

Part of the display portion 9631 a can be a touch panel region 9632 a,and data can be input by touching operation keys 9638 that aredisplayed. Note that, as an example, half of the area of the displayportion 9631 a has only a display function and the other half of thearea has a touch panel function. However, the structure of the displayportion 9631 a is not limited to this, and all the area of the displayportion 9631 a may have a touch panel function. For example, all thearea of the display portion 9631 a can display keyboard buttons andserve as a touch panel while the display portion 9631 b can be used as adisplay screen.

As in the display portion 9631 a, part of the display portion 9631 b canbe a touch panel region 9632 b. When a keyboard display switching button9639 displayed on the touch panel is touched with a finger, a stylus, orthe like, a keyboard can be displayed on the display portion 9631 b.

Touch input can be performed in the touch panel region 9632 a and thetouch panel region 9632 b at the same time.

The switch 9626 for switching a display mode allows switching between alandscape mode and a portrait mode, color display and black-and-whitedisplay, and the like. The power saver switch 9625 can control displayluminance in accordance with the amount of external light in use of thetablet terminal 9600, which is measured with an optical sensorincorporated in the tablet terminal 9600. In addition to the opticalsensor, other detecting devices such as sensors for determininginclination, such as a gyroscope or an acceleration sensor, may beincorporated in the tablet terminal.

Although the display portion 9631 a and the display portion 9631 b havethe same display size in FIG. 20A, one embodiment of the presentinvention is not limited to this example. The display portion 9631 a andthe display portion 9631 b may have different sizes or different displayquality. For example, one of the display portions may display higherdefinition images than the other.

The tablet terminal is closed in FIG. 20B. The tablet terminal includesthe housing 9630, a solar cell 9633, and a charge and discharge controlcircuit 9634 including a DC-DC converter 9636. The power storage unit ofone embodiment of the present invention is used as the power storageunit 9635.

The tablet terminal 9600 can be folded in two so that the housings 9630a and 9630 b overlap with each other when not in use. Thus, the displayportions 9631 a and 9631 b can be protected, which increases thedurability of the tablet terminal 9600. In addition, the power storageunit 9635 of one embodiment of the present invention has flexibility andcan be repeatedly bent without a large decrease in charge and dischargecapacity. Thus, a highly reliable tablet terminal can be provided.

The tablet terminal illustrated in FIGS. 20A and 20B can also have afunction of displaying various kinds of data, such as a calendar, adate, or the time, on the display portion as a still image, a movingimage, and a text image, a function of displaying, a touch-inputfunction of operating or editing data displayed on the display portionby touch input, a function of controlling processing by various kinds ofsoftware (programs), and the like.

The solar cell 9633, which is attached on the surface of the tabletterminal, supplies electric power to a touch panel, a display portion,an image signal processor, and the like. Note that the solar cell 9633can be provided on one or both surfaces of the housing 9630 and thepower storage unit 9635 can be charged. The use of a lithium-ion batteryas the power storage unit 9635 brings an advantage such as a reductionin size.

The structure and the operation of the charge and discharge controlcircuit 9634 illustrated in FIG. 20B will be described with reference toa block diagram in FIG. 20C. The solar cell 9633, the power storage unit9635, the DC-DC converter 9636, a converter 9637, switches SW1 to SW3,and the display portion 9631 are illustrated in FIG. 20C, and the powerstorage unit 9635, the DC-DC converter 9636, the converter 9637, and theswitches SW1 to SW3 correspond to the charge and discharge controlcircuit 9634 in FIG. 20B.

First, an example of operation in the case where power is generated bythe solar cell 9633 using external light is described. The voltage ofelectric power generated by the solar cell is raised or lowered by theDC-DC converter 9636 to a voltage for charging the power storage unit9635. When the display portion 9631 is operated with the power from thesolar cell 9633, the switch SW1 is turned on and the voltage of thepower is raised or lowered by the converter 9637 to a voltage needed foroperating the display portion 9631. When display on the display portion9631 is not performed, the switch SW1 is turned off and the switch SW2is turned on, so that the power storage unit 9635 can be charged.

Note that the solar cell 9633 is described as an example of a powergeneration means; however, one embodiment of the present invention isnot limited to this example. The power storage unit 9635 may be chargedusing another power generation means such as a piezoelectric element ora thermoelectric conversion element (Peltier element). For example, thepower storage unit may be charged with a non-contact power transmissionmodule capable of performing charging by transmitting and receivingelectric power wirelessly (without contact), or any of the other chargemeans used in combination.

FIG. 21 illustrates examples of other electronic devices. In FIG. 21, adisplay device 8000 is an example of an electronic device including apower storage device 8004 of one embodiment of the present invention.Specifically, the display device 8000 corresponds to a display devicefor TV broadcast reception and includes a housing 8001, a displayportion 8002, speaker portions 8003, and the power storage device 8004.The power storage device 8004 of one embodiment of the present inventionis provided in the housing 8001. The display device 8000 can receiveelectric power from a commercial power supply. Alternatively, thedisplay device 8000 can use electric power stored in the power storagedevice 8004. Thus, the display device 8000 can be operated with the useof the power storage device 8004 of one embodiment of the presentinvention as an uninterruptible power supply even when electric powercannot be supplied from a commercial power supply due to power failureor the like.

A semiconductor display device such as a liquid crystal display device,a light-emitting device in which a light-emitting element such as anorganic EL element is provided in each pixel, an electrophoresis displaydevice, a digital micromirror device (DMD), a plasma display panel(PDP), or a field emission display (FED) can be used for the displayportion 8002.

Note that the display device is any of all of information displaydevices for personal computers, advertisement displays, and the likebesides TV broadcast reception.

In FIG. 21, an installation lighting device 8100 is an example of anelectronic device including a power storage device 8103 of oneembodiment of the present invention. Specifically, the lighting device8100 includes a housing 8101, a light source 8102, and a power storagedevice 8103. Although FIG. 21 illustrates the case where the powerstorage device 8103 is provided in a ceiling 8104 on which the housing8101 and the light source 8102 are installed, the power storage device8103 may be provided in the housing 8101. The lighting device 8100 canreceive electric power from a commercial power supply. Alternatively,the lighting device 8100 can use electric power stored in the powerstorage device 8103. Thus, the lighting device 8100 can be operated withthe use of the power storage device 8103 of one embodiment of thepresent invention as an uninterruptible power supply even when electricpower cannot be supplied from a commercial power supply due to powerfailure or the like.

Note that although the installation lighting device 8100 provided in theceiling 8104 is illustrated in FIG. 21 as an example, the power storagedevice of one embodiment of the present invention can be used in aninstallation lighting device provided in, for example, a wall 8105, afloor 8106, a window 8107, or the like other than the ceiling 8104.Alternatively, the power storage device can be used in a tabletoplighting device or the like.

As the light source 8102, an artificial light source which emits lightartificially by using electric power can be used. Specifically, anincandescent lamp, a discharge lamp such as a fluorescent lamp, andlight-emitting elements such as an LED and an organic EL element aregiven as examples of the artificial light source.

In FIG. 21, an air conditioner including an indoor unit 8200 and anoutdoor unit 8204 is an example of an electronic device including apower storage device 8203 of one embodiment of the present invention.Specifically, the indoor unit 8200 includes a housing 8201, an airoutlet 8202, the power storage device 8203, and the like. Although FIG.21 illustrates the case where the power storage device 8203 is providedin the indoor unit 8200, the power storage device 8203 may be providedin the outdoor unit 8204. Alternatively, the power storage device 8203may be provided in both the indoor unit 8200 and the outdoor unit 8204.The air conditioner can receive electric power from the commercial powersource. Alternatively, the air conditioner can use electric power storedin the power storage device 8203. Particularly in the case where thepower storage devices 8203 are provided in both the indoor unit 8200 andthe outdoor unit 8204, the air conditioner can be operated with the useof the power storage device 8203 of one embodiment of the presentinvention as an uninterruptible power source even when electric powercannot be supplied from a commercial power source due to power failureor the like.

Note that although the separated air conditioner including the indoorunit and the outdoor unit is shown in FIG. 21 as an example, the powerstorage device of one embodiment of the present invention can be used inan air conditioner in which the functions of an indoor unit and anoutdoor unit are integrated in one housing.

In FIG. 21, an electric refrigerator-freezer 8300 is an example of anelectronic device including a power storage device 8304 of oneembodiment of the present invention. Specifically, the electricrefrigerator-freezer 8300 includes a housing 8301, a door for arefrigerator 8302, a door for a freezer 8303, and the power storagedevice 8304. The power storage device 8304 is provided in the housing8301 in FIG. 21. The electric refrigerator-freezer 8300 can receiveelectric power from a commercial power supply. Alternatively, theelectric refrigerator-freezer 8300 can use electric power stored in thepower storage device 8304. Thus, the electric refrigerator-freezer 8300can be operated with the use of the power storage device 8304 of oneembodiment of the present invention as an uninterruptible power supplyeven when electric power cannot be supplied from a commercial powersupply due to power failure or the like.

Note that among the electronic devices described above, a high-frequencyheating apparatus such as a microwave oven and an electronic device suchas an electric rice cooker require high power in a short time. Thetripping of a breaker of a commercial power supply in use of anelectronic device can be prevented by using the power storage device ofone embodiment of the present invention as an auxiliary power supply forsupplying electric power which cannot be supplied enough by a commercialpower supply.

In addition, in a time period when electronic devices are not used,particularly when the proportion of the amount of electric power whichis actually used to the total amount of electric power which can besupplied from a commercial power supply source (such a proportionreferred to as a usage rate of electric power) is low, electric powercan be stored in the power storage device, whereby the usage rate ofelectric power can be reduced in a time period when the electronicdevices are used. For example, in the case of the electricrefrigerator-freezer 8300, electric power can be stored in the powerstorage device 8304 in night time when the temperature is low and thedoor for a refrigerator 8302 and the door for a freezer 8303 are notoften opened or closed. Then, in daytime when the temperature is highand the door for a refrigerator 8302 and the door for a freezer 8303 arefrequently opened and closed, the power storage device 8304 is used asan auxiliary power supply; thus, the usage rate of electric power indaytime can be reduced.

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Embodiment 6

In this embodiment, examples of vehicles using power storage deviceswill be described.

The use of a power storage device in vehicles can lead tonext-generation clean energy vehicles such as hybrid electric vehicles(HEVs), electric vehicles (EVs), and plug-in hybrid electric vehicles(PHEVs).

FIGS. 22A and 22B each illustrate an example of a vehicle using oneembodiment of the present invention. An automobile 8400 illustrated inFIG. 22A is an electric vehicle which runs on the power of the electricmotor. Alternatively, the automobile is a hybrid electric vehiclecapable of driving using either the electric motor or the engine asappropriate. One embodiment of the present invention achieves ahigh-mileage vehicle. The automobile 8400 includes a power storagedevice. The power storage device is used not only for driving theelectric motor 8206, but also for supplying electric power to alight-emitting device such as a headlight 8401 or a room light (notillustrated).

The power storage device can also supply electric power to a displaydevice included in the automobile 8400, such as a speedometer or atachometer. Furthermore, the power storage device can supply electricpower to a semiconductor device included in the automobile 8400, such asa navigation system.

FIG. 22B illustrates an automobile 8500 including a power storagedevice. The automobile 8500 can be charged when the power storage deviceis supplied with electric power through external charging equipment by aplug-in system, a contactless power feeding system, or the like. In FIG.22B, the power storage device included in the automobile 8500 is chargedwith the use of a ground-based charging apparatus 8021 through a cable8022. In charging, a given method such as CHAdeMO (registered trademark)or Combined Charging System may be employed as a charging method, thestandard of a connector, or the like as appropriate. The chargingapparatus 8021 may be a charging station provided in a commerce facilityor a power source in a house. For example, with the use of a plug-intechnique, a power storage device 8024 included in the automobile 8500can be charged by being supplied with electric power from outside. Thecharging can be performed by converting AC electric power into DCelectric power through a converter such as an AC-DC converter.

Further, although not illustrated, the vehicle may include a powerreceiving device so as to be charged by being supplied with electricpower from an above-ground power transmitting device in a contactlessmanner. In the case of the contactless power supply system, by fittingthe power transmitting device in a road or an exterior wall, chargingcan be performed not only when the electric vehicle is stopped but alsowhen driven. In addition, the contactless power supply system may beutilized to perform transmission/reception between vehicles.Furthermore, a solar cell may be provided in the exterior of theautomobile to charge the power storage device when the automobile stopsor moves. To supply electric power in such a contactless manner, anelectromagnetic induction method or a magnetic resonance method can beused.

According to one embodiment of the present invention, the power storagedevice can have improved cycle characteristics and reliability.Furthermore, according to one embodiment of the present invention, thepower storage device itself can be made more compact and lightweight asa result of improved characteristics of the power storage device. Thecompact and lightweight power storage device contributes to a reductionin the weight of a vehicle, and thus increases the driving distance.Further, the power storage device included in the vehicle can be used asa power source for supplying electric power to products other than thevehicle. In such a case, the use of a commercial power source can beavoided at peak time of electric power demand.

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Example 1

In this example, a forming method and measurement results of thenegative electrode active material of one embodiment of the presentinvention are described.

[Formation of Negative Electrode Active Material]

First, samples 111 to 113 that are to be the negative electrode activematerials were formed. As a raw material, silicon monoxide (SiO) powderwas used.

The silicon monoxide powder was baked in a baking furnace. The bakingwas performed under conditions shown in Table 1. Table 1 shows thetemperature rising rate from a room temperature to a target temperatureand the treatment time at the target temperature. For example, thetreatment was performed on the sample 111 during a period when thetemperature was raised from a room temperature to 1,000° C. at atemperature rising rate of 240° C./hour and then maintained at 1,000° C.for 3 hours. The baking is performed in a nitrogen atmosphere.

TABLE 1 Treatment Temperature rising rate Target temperature time Sample111 240° C./hr. 1000° C. 3 hr. Sample 112 240° C./hr. 1100° C. 3 hr.Sample 113 240° C./hr. 1200° C. 3 hr.

After the baking, crushing was performed with a mortar.

[XRD Observation]

The samples 111 to 113 subjected to the baking were observed with X-raydiffraction (XRD). The results of XRD are shown in FIGS. 24A to 24C.FIGS. 24A, 24B, and 24C show the results of the sample 111, the sample112, and the sample 113, respectively. Here, a peak at around 2θ=28°, apeak at around 2θ=47°, and a peak at around 2θ=56° correspond to a (111)plane, a (220) plane, and a (311) plane, respectively.

The crystallite size of silicon was calculated from analysis of theobtained XRD results. The crystallite size was calculated by Rietveldanalysis. As analysis software, TOPAS (DIFFRAC^(plus) TOPAS Version 3)manufactured by Broker AXS was used. The structure of the space groupF-43m was used for Rietveld analysis, and fitting was performed, so thatthe lattice constant and the crystallite size were calculated. Theobtained crystallite sizes of the samples 111, 112, and 113 were 3.2.nm, 6.7 nm, and 12 nm, respectively. The obtained lattice constants ofthe samples 111, 112, and 113 were 0.53687 nm, 0.54175 nm, and 0.54279nm, respectively.

[Cross-sectional TEM Observation]

Next, the obtained, samples 111 to 113 were observed with scanningtransmission electron microscopy (STEM) and transmission electronmicroscopy (TEM). As an STEM apparatus, HD-2300 manufactured by HitachiHigh-Technologies Corporation was used. As a TEM apparatus, H-9500manufactured by Hitachi High-Technologies Corporation was used. Theaccelerating voltage was 300 kV. FIGS. 25A to 25C, FIG. 26A, FIGS. 27Aand 27B, FIG. 28A, FIGS. 29A and 29B, and FIG. 30A show results of theobservation.

FIGS. 25A to 25C show observation results of the sample 111. FIG. 25Ashows the observation result with STEM at a magnification of 30,000times, and FIG. 25B shows the observation result, with STEM at amagnification of 500,000 times, of a region enclosed by a dashed line inFIG. 25A. FIG. 25C shows the observation result, with TEM at amagnification of 8,000,000 times, of a region enclosed by a dashed linein FIG. 25B. FIG. 26A shows the observation result, with TEM at amagnification of 8,000,000 times, of a region different from that shownin FIGS. 25A to 25C. A darker portion than others in FIG. 25C or FIG.26A is estimated to have a crystal of silicon. In FIG. 26A, a latticeimage is clearly observed in a darker portion.

FIG. 26B shows a selected area diffraction pattern of the sample 111. Asshown in FIG. 26B, three rings are observed. Analysis with the use of acamera constant suggested that the three rings corresponded to a (111)plane, a (220) plane, and a (311) plane of silicon in order from theinside.

FIGS. 27A and 27B and FIG. 28A show observation results of the sample112. FIG. 27A shows the observation result with TEM at a magnificationof 400,000 times, FIG. 27B shows the observation result at amagnification of 4,000,000 times, and FIG. 28A shows the observationresult at a magnification of 8,000,000 times. In FIG. 28A, a latticeimage is clearly observed. FIG. 28B shows a selected area diffractionpattern of the sample 112. As in FIG. 26B, three rings are observed.

FIGS. 29A and 29B and FIG. 30A show observation results of the sample113. FIG. 29A shows the observation result with TEM at a magnificationof 400,000 times, FIG. 29B shows the observation result at amagnification of 4,000,000 times, and FIG. 30A shows the observationresult at a magnification of 8,000,000 times. In FIG. 30A, a latticeimage is clearly observed. As compared with the sample 112, it issuggested that the sample 113 has a large crystal region. FIG. 30B showsa selected area diffraction pattern of the sample 113. In FIG. 30B,spots are arranged in a ring pattern. The observation of the samples 111to 113 with selected area diffraction was performed on a region withapproximately 300 nmφ.

[Measurement of Particle Size]

Particle sizes were measured using a laser diffraction particle sizeanalyzer (SALD-2200 manufactured by Shimadzu Corporation). A laserdiffraction and scattering method was used as a method for calculatingthe particle size. Table 2 shows the average particle sizes and thevalues of D90 (the particle size when the integrated amount of particlesize distribution in the accumulated particle curve obtained as a resultof particle size measurement is 90%).

TABLE 2 Average particle size [μm] Standard deviation [μm] D90 [μm]Sample 111 3.41 0.476 17.39 Sample 112 3.78 0.476 14.81 Sample 113 3.840.497 15.85

As shown in Table 2, the obtained average particle sizes of the sample111, the sample 112, and the sample 113 were 3.41 μm, 3.78 μm, and 3.84μm, respectively.

Example 2

In this embodiment, measurement results of a power storage device formedusing the negative electrode active material shown in Example 1 aredescribed.

[Formation of Electrode]

An electrode was formed using the negative electrode active materialobtained in Example 1. Acetylene black (AB) was used as a conductiveadditive, and a precursor of polyimide was used as a binder. Compositionof the electrode was adjusted so that the proportion of the sample 111to AB to the precursor of polyimide was 80:5:15 (weight %).

Next, methods for forming the electrodes will be described. FIG. 31shows a flow of the formation method. The negative electrode activematerial and AB were weighed and mixed to obtain a mixture A (Step S1).Next, the mixture A was stirred with a mixer (a planetary centrifugalmixer “THINKY MIXER” manufactured by THINKY CORPORATION) and NMP wasadded thereto as a solvent in several parts to obtain a mixture B (StepS2). Here, when the amount of added NMP is reduced and adjusted so thatthe viscosity of the mixture B is high, mixing (kneading) with a mixerlater can be performed on the mixture with high viscosity. The kneadingcan weaken cohesion of the active material, and increase dispersibilityof the active material and AB.

Next, the mixture B was kneaded with a mixer. Five-minute treatment at2000 rpm was performed 5 times to obtain a mixture C (Step S3).

Next, the precursor of polyimide was added, and mixing with a mixer wasperformed. Five-minute treatment, at 2000 rpm was performed three timesto obtain a mixture D (Step S4). The proportion of the solid content ofthe mixture D was 67%. The proportion of the solid content means theproportion of the weight of materials other than the solvent (the weightsum of the active material, AB, and the precursor of polyimide) to thetotal weight of the mixture D. Note that 13.7% of the used precursor ofpolyimide was imidized to be polyimide through heat treatment.

Next, a copper current collector (with a thickness of 18 μm) providedwith graphite as an undercoat was prepared. Next, the obtained mixture Dwas applied to a surface of the current collector provided with theundercoat. A blade method was used for the application. The distancebetween the blade and the current collector was set to 100 μm.

After that, treatment for volatilizing the solvent was performed for 2hours at 80° C. in a reduced-pressure atmosphere with a vacuum dryer,and then heat treatment was performed for 5 hours at 200° C. in areduced-pressure atmosphere with a small vacuum-atmosphere furnaceHV-13C manufactured by MOTOYAMA. Through the above steps, the electrodeincluding the negative electrode active material was formed.

The electrodes including the sample 111, the sample 112, and the sample113 as their negative electrode active materials are referred to as anelectrode 111, an electrode 112, and an electrode 113, respectively.

[Fabrication of Storage Batteries]

Next, as a counter electrode, lithium metal was combined with each ofthe electrodes 111 to 113 to form a half cell. Plural regions werestamped out from the electrodes, and two or three half cells wereformed. The thickness and the amount of the active material in each ofthe electrodes used for the half cells are shown in Table 3.

TABLE 3 Electrode Amount of Thickness active material of electrode Type[mg/cm²] [μm] Storage battery 111-1 Electrode 111 2.0 33 Storage battery111-2 Electrode 111 2.0 36 Storage battery 111-3 Electrode 111 2.0 42Storage battery 112-1 Electrode 112 2.1 33 Storage battery 112-2Electrode 112 2.0 37 Storage battery 113-1 Electrode 113 1.9 49 Storagebattery 113-2 Electrode 113 1.9 47 Storage battery 113-3 Electrode 1131.9 48

As shown in Table 3, storage batteries 111-1 to 111-3 were formed usingthe electrode 111. Similarly, storage batteries 112-1 and 112-2 wereformed using the electrode 112, and storage batteries 113-1 to 113-3were formed using the electrode 113. The amount of active material ofeach of the electrodes 111 to 113 was approximately 2.0 mg/cm².

Coin-type storage batteries (CR2032 type, with a diameter of 20 mm and aheight of 3.2 mm) were used as the storage batteries. For a separator, astack of polypropylene and GF/C, which is glass-fiber filter papermanufactured by Whatman, was used. An electrolytic solution was formedin such a manner that lithium hexafluorophosphate (LiPF₆) was dissolvedat a concentration of 1 mol/L in a solution in which ethylene carbonate(EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 3:7. Apositive electrode can and a negative electrode can were formed ofstainless steel (SUS).

[Measurement of Storage Batteries]

Next, the formed half cells were charged and discharged. The measurementtemperature was 25° C. Conditions for the charge and discharge wereexplained below. The discharge (Li reception) was performed in thefollowing manner: constant current discharge was performed at 180 mA/gwith the lower limit set to 0.01 V, and then, constant voltage dischargewas performed at 0.01 V with the lower limit set to a current valuecorresponding to 18 mA/g. The charge (Li release) was performed byconstant current charge at 180 mA/g with the upper limit set to 2.5 V. A1-hour break was taken after the charge and discharge. The break meansthe battery is held without voltage application. The storage battery111-3, the storage battery 112-2, and the storage battery 113-3 werecharged and discharged only in one cycle. Charge and discharge cycleperformances of the other storage batteries were measured. The chargeand discharge cycle performances are described later.

The charge-discharge curve of the storage battery 111-3 is shown in FIG.32A, the charge-discharge curve of the storage battery 112-2 is shown inFIG. 32B, and the charge-discharge curve of the storage battery 113-3 isshown in FIG. 33. Here, the charge capacity and the discharge capacitywere normalized with the weight of the active material.

[SEM Observation]

After charge and discharge were performed in one cycle, the storagebattery 111-3, the storage battery 112-2 and the storage battery 113-3were deconstructed and the electrodes were taken out and observed withscanning electron microscopy (SEM). The observation results are shown inFIGS. 34A to 34C, FIGS. 35A to 35C, and FIGS. 36A to 36C. FIGS. 34A and34B shove observation results of the electrode 111 of the storagebattery 111-3, FIGS. 35A and 35B show observation results of theelectrode 112 of the storage battery 112-2, and FIGS. 36A and 36B showobservation results of the electrode 113 of the storage battery 113-3.FIG. 34C shows an observation result of the electrode 111 not subjectedto charge and discharge, FIG. 35C shows an observation result of theelectrode 112 not subjected to charge and discharge, and FIG. 36C showsan observation result of the electrode 113 not subjected to charge anddischarge.

In the half cell using the active material where the crystallite size ofsilicon is 6.7 nm or 12 nm, a crack of a particle of the active materialwas observed as shown in a region surrounded by a dashed line in FIG.35A or FIG. 36A, respectively. FIG. 35B and FIG. 36B are enlarged viewof FIG. 35A and FIG. 36A. It is estimated that the crack of the particlewas generated because of expansion and contraction of silicon at thetime of charge and discharge. In contrast, under a condition where thecrystallite size of silicon was 3.2 nm, a crack of a particle of theactive material was not observed. Because the crystallite size ofsilicon is small, it is estimated that, in the active material, a stressgenerated by expansion and contraction of silicon at the time of chargeand discharge can be reduced by a region (e.g., a region includingsilicon oxide) at the periphery of a portion expanded and contracted.

The charge and discharge cycle performances of the storage batteries111-1 and 111-2 are shown in FIG. 37A, and the performances of thestorage battery 112-1 is shown in FIG. 37B, and the performance of thestorage batteries 113-1 and 113-2 are shown in FIG. 37C. In FIGS. 37A to37C, the horizontal axis represents the number of times of charge anddischarge, and the vertical axis represents the charge capacity (thecapacity at the time of Li release). The charge capacity was normalizedby weight of the active material. Under the condition where thecrystallite size of silicon was 3.2 nm or 6.7 nm, decrease in capacitywas suppressed and the cycle performances were excellent as comparedwith the condition of 12 nm.

Charge and discharge efficiency of each cycle is shown in FIGS. 38A to38C. Note that the charge and discharge efficiency means [(chargecapacity/discharge capacity)×100] [%]. The shift of the charge anddischarge efficiency caused by charge and discharge cycles in thestorage batteries 111-1 and 111-2 are shown in FIG. 38A, and the shiftin the storage battery 112-1 is shown in FIG. 38B, and the shift in thestorage batteries 113-1 and 113-2 are shown in FIG. 38C. The averagecharge and discharge efficiency in 11 to 15 cycles was calculated, andthe average value was 99.7% in the storage battery 111-1, 99.8% in thestorage battery 111-2, 99.2% in the storage battery 112-1, 98.8% in thestorage battery 113-1, and 99.0% in the storage battery 113-2. When thecrystallite size of silicon was 3.2 nm, that is, in the storagebatteries 111-1 and 111-2, the charge and discharge efficiency washigher and more excellent.

REFERENCE NUMERALS

100: negative electrode material, 101: region, 102: region, 103: region,200: negative electrode, 201: negative electrode current collector, 202:negative electrode active material layer, 300: storage battery, 301:positive electrode can, 302: negative electrode can, 303: gasket, 304:positive electrode, 305: positive electrode current collector, 306:positive electrode active layer, 307: negative electrode, 308: negativeelectrode current collector, 309: negative electrode active materiallayer, 310: separator, 500: storage battery, 501: positive electrodecurrent collector, 502: positive electrode active material layer, 503:positive electrode, 504: negative electrode current collector, 505:negative electrode active material layer, 506: negative electrode, 507:separator, 508: electrolytic solution, 509: exterior body, 510: positiveelectrode lead electrode, 511: negative electrode lead electrode, 512:welding region, 513: bent portion, 514: scaling member, 521: grapheneflake, 522: positive electrode active material, 600: storage battery,601: positive electrode cap, 602: battery can, 603: positive electrodeterminal, 604: positive electrode, 605: separator, 606: negativeelectrode, 607: negative electrode terminal, 608: insulating plate, 609:insulating plate, 611: PTC element, 612: safety valve mechanism, 900:circuit board, 910: label, 911: terminal, 912: circuit, 913: storagebattery, 914: antenna, 915: antenna, 916: layer, 917: layer, 918:antenna, 919: terminal, 920: display device, 921: sensor, 922: terminal,951: terminal, 952: terminal, 981: film, 982: film, 990: storagebattery, 991: exterior body, 992: exterior body, 993: wound body, 994:negative electrode, 995: positive electrode, 996: separator, 997: leadelectrode, 998: lead electrode, 1122: charger, 1123: load, 1500:secondary battery, 1700: curved surface, 1701: plane, 1702: curve, 1703:radius of curvature, 1704: center of curvature, 1800: center ofcurvature, 1801: film, 1802: radius of curvature, 1803: film, 1804:radius of curvature, 1805: component including electrodes and anelectrolytic solution, 7100: portable display device, 7101: housing,7102: display portion, 7103: operation button, 7104: power storagedevice, 7200: portable information terminal, 7201: housing, 7202:display portion, 7203: band, 7204: buckle, 7205: operation button, 7206:input output terminal, 7207: icon, 7300: display device, 7304: displayportion, 7400: cellular phone, 7401: housing, 7402: display portion,7403: operation button, 7404: external connection port, 7405: speaker,7406: microphone, 7407: power storage device, 8000: display device,8001: housing, 8002: display portion, 8003: speaker portion, 8004: powerstorage device, 8021: charging apparatus, 8022: cable, 8024: powerstorage device, 8100: lighting device, 8101: housing, 8102: lightsource, 8103: power storage device, 8014: ceiling, 8105: wall, 8106:floor, 8107: window, 8200: indoor unit, 8201: housing, 8202: air outlet,8203: power storage device, 8204: outdoor unit, 8206: electric motor,8300: electric refrigerator-freezer, 8301: housing, 8302: door for arefrigerator, 8303: door for a freezer, 8304: power storage device,8400: automobile, 8401: headlight, 8500: automobile, 9600: tabletterminal, 9625: switch, 9626: switch, 9627: power switch, 9628:operation switch, 9629: fastener, 9630: housing, 9630 a: housing, 9630b: housing, 9631: display portion, 9631 a: display portion, 9631 b:display portion, 9632 a: region, 9632 b: region, 9633: solar cell, 9634:charge and discharge control circuit, 9635: power storage unit, 9636:DC-DC converter, 9637; converter, 9638: operation key, 9639: button,9640: movable portion.

This application is based on Japanese Patent Application serial no.2014-107441 filed with Japan Patent Office on May 23, 2014, the entirecontents of which are hereby incorporated by reference.

What is claimed is:
 1. A method of manufacturing a negative electrodeactive material, comprising: heating a composition including SiO powderby laser light to form a first region and a second region in thecomposition, wherein: the first region includes crystalline silicon, andthe second region includes silicon oxide.
 2. The method according toclaim 1, further comprising: cooling the composition after the step ofheating.
 3. The method according to claim 2, wherein rapid cooling isperformed in the step of cooling the composition so that siliconcrystals are discretely formed.
 4. The method according to claim 2,wherein rapid cooling is performed in the step of cooling thecomposition so that distorted silicon is formed.
 5. The method accordingto claim 1, wherein the laser light is one of excimer laser light with awavelength of 400 nm or less, second harmonic of YAG laser, thirdharmonic of YAG laser, second harmonic of YVO₄ laser, and third harmonicof YVO₄ laser.
 6. The method according to claim 1, wherein thecomposition further includes a third region including amorphous siliconafter the step of heating.
 7. The method according to claim 1, wherein:a crystallite size of the crystalline silicon is larger than or equal to1 nm and smaller than or equal to 10 nm, and particle size of thenegative electrode active material is larger than or equal to 30 nm andsmaller than or equal to 30 nm.
 8. A method of manufacturing a negativeelectrode, comprising: adding a binder and a conductive additive to thenegative electrode active material manufactured by the method accordingto claim 1 to form a mixture; mixing the mixture with a solvent to forma slurry; applying the slurry onto a negative electrode currentcollector; and volatilizing the solvent.
 9. A method of manufacturing anegative electrode active material, comprising: heating a compositionincluding silicon and oxygen by laser light to form a first region and asecond region in the composition, wherein: the first region includescrystalline silicon, and the second region includes silicon oxide. 10.The method according to claim 9, further comprising: cooling thecomposition after the step of heating.
 11. The method according to claim10, wherein rapid cooling is performed in the step of cooling thecomposition so that silicon crystals are discretely formed.
 12. Themethod according to claim 10, wherein rapid cooling is performed in thestep of cooling the composition so that distorted silicon is formed. 13.The method according to claim 9, wherein the laser light is one ofexcimer laser light with a wavelength of 400 nm or less, second harmonicof YAG laser, third harmonic of YAG laser, second harmonic of YVO₄laser, and third harmonic of YVO₄ laser.
 14. The method according toclaim 9, wherein the composition further includes a third regionincluding amorphous silicon after the step of heating.
 15. The methodaccording to claim 9, wherein: a crystallite size of the crystallinesilicon is larger than or equal to 1 nm and smaller than or equal to 10nm, and particle size of the negative electrode active material islarger than or equal to 30 nm and smaller than or equal to 30 nm.
 16. Amethod of manufacturing a negative electrode, comprising: adding abinder and a conductive additive to the negative electrode activematerial manufactured by the method according to claim 9 to form amixture; mixing the mixture with a solvent to form a slurry; applyingthe slurry onto a negative electrode current collector; and volatilizingthe solvent.